Herbicidal substituted triazolinones

ABSTRACT

Herbicidally active substituted triazolinones of the formula ##STR1## in which R 1  represents hydrogen, alkyl, alkenyl, alkinyl, halogenoalkyl, halogenoalkenyl, halogenoalkinyl, alkoxyalkyl, cycloalkyl, cycloalkylalkyl, or represents tetrahydrofuranyl, tetrahydrofuranylalkyl, or represents in each case optionally substituted aralkyl or aryl, 
     R 2  represents hydrogen, alkyl, alkenyl, alkinyl, halogenoalkyl, halogenoalkenyl, halogenoalkinyl, cyanoalkyl, hydroxyalkyl, alkoxyalkyl, alkoxycarbonylalkyl, alkoxycarbonylalkenyl, alkylaminoalkyl, dialkylaminoalkyl, or represents in each case optionally substituted cycloalkyl, cycloalkylalkyl, cycloalkenyl or cycloalkenylalkyl, or represents optionally substituted heterocyclylalkyl, or represents in each case optionally substituted aralkyl, aroyl, aryl, aralkyloxy or aryloxy, or represents alkoxy, alkenyloxy or alkinyloxy, 
     X represents oxygen or sulphur and 
     Y represents oxygen or sulphur. 
     New intermediates therefor are also shown.

This application is a continuation in part of application Ser. No.409,175, filed Sep. 19, 1989, now abandoned, which is acontinuation-in-part of application Ser. No. 200,995, filed May 31,1988, now abandoned, and it is a continuation-in-part of applicationSer. No. 433,650, filed Nov. 8, 1989, now abandoned.

It is known that certain substituted triazolinones, such as, forexample, the compound4-amino-1-(N-isopropylcarbamoyl)-3-methylthio-(1H,4H)-1,2,4-triazolin-5-oneor the compound4-amino-1-(N-propylcarbamoyl)-3-methylthio-(1H,4H)-1,2,4-triazolin-5-oneor the compound 4-amino-1-(N-butylcarbamoyl)-3-methylthio-(1H,4H)-1,2,4-triazolin-5-one or the compound4-amino-1-(N-cyclohexylcarbamoyl)-3-methylthio-(1H,4H)-1,2,4-triazolin-5-one(cf., for example, JP 52/125,168), have herbicidal properties.

It has been disclosed that certain nitrogen heterocycles such as, forexample, 4-amino-3-methyl-6-phenyl-1,2,4-triazin-5-one orN-isobutyl-2-oximidazolidine-1-carboxamide (compare, for example, DE-OS(German Published Specification) 2,364,474 and R. Wegler "Chemie derPflanzenschutz- und Schadlingsbekampfungsmittel, Vol. 5, 219 (1977))possess herbicidal properties.

However, the herbicidal activity of these previously known compoundswith respect to problem weeds as well as their tolerability with respectto important cultivated plants is not completely satisfactory in allareas of application. Furthermore, certain substituted triazolinones,such as, for example,1-(N,N-dimethylcarbamoyl)-3-phenyl-4-amino-1,2,4-triazolin-5-one havebeen disclosed (compare J. Heterocycl. Chem. 17, 1691-1696 [1980]; Org.Mass. Spectrom. 14, 369-378 [1979]). Nothing has hitherto been disclosedabout a herbicidal activity of these previously known triazolinones.

New substituted triazolinones of the general formula (I) ##STR2## inwhich R¹ represents hydrogen, alkyl, alkenyl, alkinyl, halogenoalkyl,halogenoalkenyl, halogenoalkinyl, alkoxyalkyl, cycloalkyl,cycloalkylalkyl, or represents tetrahydrofuranyl,tetrahydrofuranylalkyl, or represents in each case optionallysubstituted aralkyl or aryl,

R² represents hydrogen, alkyl, alkenyl, alkinyl, halogenoalkyl,halogenoalkenyl, halogenoalkinyl, cyanoalkyl, hydroxyalkyl, alkoxyalkyl,alkoxycarbonylalkyl, alkoxycarbonylalkenyl, alkylaminoalkyl,dialkylaminoalkyl, or represents in each case optionally substitutedcycloalkyl, cycloalkylalkyl, cycloalkenyl or cycloalkenylalkyl, orrepresents optionally substituted heterocyclylalkyl, or represents ineach case optionally substituted aralkyl, aroyl, aryl, aralkyloxy oraryloxy, or represents alkoxy, alkenyloxy or alkinyloxy,

X represents oxygen or sulphur and

Y represents oxygen or sulphur,

have been found.

The compounds of the formula (I) can optionally exist as geometricand/or optical isomers or isomer mixtures of different composition,depending on type of the substituents R¹ and R². Both the pure isomersand the isomer mixtures are claimed according to the invention.

Furthermore, it has been found that the new substituted triazolinones ofthe general formula (I) ##STR3## in which R¹ represents hydrogen, alkyl,alkenyl, alkinyl, halogenoalkyl, halogenoalkenyl, halogenoalkinyl,alkoxyalkyl, cycloalkyl, cycloalkylalkyl, or representstetrahydrofuranyl, tetrahydrofuranylalkyl, or represents in each caseoptionally substituted aralkyl or aryl,

R² represents hydrogen, alkyl, alkenyl, alkinyl, halogenoalkyl,halogenoalkenyl, halogenoalkinyl, cyanoalkyl, hydroxyalkyl, alkoxyalkyl,alkoxycarbonylalkyl, alkoxycarbonylalkenyl, alkylaminoalkyl,dialkylaminoalkyl, or represents in each case optionally substitutedcycloalkyl, cycloalkylalkyl, cycloalkenyl or cycloalkenylalkyl, orrepresents optionally substituted heterocyclylalkyl, or represents ineach case optionally substituted aralkyl, aroyl, aryl, aralkyloxy oraryloxy, or represents alkoxy, alkenyloxy or alkinyloxy,

X represents oxygen or sulphur and

Y represents oxygen or sulphur,

are obtained when

(a) hydrazones of the formula (II) ##STR4## in which R¹, R², X and Yhave the abovementioned meaning and

R³ and R⁴ independently of one another in each case represent hydrogen,alkyl, aralkyl or aryl,

are reacted with an acid, if appropriate in the presence of a diluent,or in that

b) 1H-triazolinones of the formula (III), ##STR5## in which R¹ and Xhave the above mentioned meaning, are reacted with iso(thio)cyanates ofthe formula (IV),

    R.sup.2 --N═C═Y                                    (IV)

in which R² and Y have the above mentioned meaning, if appropriate, inthe presence of a diluent and, if appropriate, in the presence of areaction auxiliary, or in that

c) triazolinones of the formula (V) ##STR6## in which R¹, X and Y havethe above mentioned meaning and

R⁵ represents alkyl, aryl or arylalkyl,

are reacted with amines of the formula (VI),

    R.sup.2 --NH.sub.2                                         (VI)

in which R² has the above mentioned meaning, if appropriate, in thepresence of a diluent and, if appropriate, in the presence of a reactionauxiliary, or when

(d) 1H-triazolinones of the formula (III) ##STR7## in which R¹ has theabovementioned meaning, are reacted with urethanes of the formula (VII)##STR8## in which R² has the abovementioned meaning and

R⁵ represents alkyl, aryl or arylalkyl, if appropriate in the presenceof a diluent and if appropriate in the presence of a reaction auxiliary.

Finally, it has been found that the new substituted triazolinones of thegeneral formula (I) possess herbicidal properties.

Surprisingly, the substituted triazolinones of the general formula (I)according to the invention show a considerably higher herbicidal potencyagainst problem weeds than the nitrogen heterocycles known from theprior art such as, for example,4-amino-3-methyl-6-phenyl-1,2,4-triazin-5-one,4-amino-1-(N-isopropylcarbamoyl)-3-methylthio-(1H,4H)-1,2,4-triazolin-5-oneor the compound4-amino-1-(N-propylcarbamoyl)-3-methylthio-(1H,4H)-1,2,4-triazolin-5-oneor the compound4-amino-1-(N-butylcarbamoyl)-3-methylthio-(1H,4H)-1,2,4-triazolin-5-oneor the compound4-amino-1-(N-cyclohexylcarbamoyl)-3-methylthio-(1H,4H)-1,2,4-triazolin-5-one,which are compounds of a similar chemical structure and a similar typeof action.

Formula (I) provides a general definition of the substitutedtriazolinones according to the invention.

Preferred compounds of the formula (I) are those in which R¹ representshydrogen, or represents in each case straight-chain or branched alkylhaving 1 to 8 carbon atoms, alkenyl having 2 to 8 carbon atoms, alkinylhaving 2 to 8 carbon atoms, halogenoalkyl having 1 to 8 carbon atoms and1 to 17 identical or different halogen atoms, halogenoalkenyl having 2to 8 carbon atoms and 1 to 15 identical or different halogen atoms,halogenoalkinyl having 2 to 8 carbon atoms and 1 to 13 identical ordifferent halogen atoms, alkoxyalkyl having 1 to 6 carbon atoms in theindividual alkyl parts, or represents cycloalkyl or cycloalkylalkyl ineach case having 3 to 7 carbon atoms in the cycloalkyl part and whereappropriate 1 to 6 carbon atoms in the straight-chain or branched alkylpart, or represents tetrahydrofuranyl, or representstetrahydrofuranylalkyl optionally having 1 to 4 carbon atoms in thestraight-chain or branched alkyl part, or represents aralkyl or aryl ineach case having 6 to 10 carbon atoms in the aryl part and whereappropriate 1 to 6 carbon atoms in the straight-chain or branched alkylpart, and which are in each case optionally monosubstituted orpolysubstituted by identical or different substituents; suitable arylsubstituents in each case being: halogen, cyano, nitro and also in eachcase straight-chain or branched alkyl, alkoxy, alkylthio, halogenoalkyl,halogenoalkoxy or halogenoalkylthio in each case having 1 to 4 carbonatoms and where appropriate 1 to 9 identical or different halogen atoms,

R² represents hydrogen, or represents in each case straight-chain orbranched alkyl having 1 to 18 carbon atoms, alkenyl having 2 to 8 carbonatoms, alkinyl having 2 to 8 carbon atoms, halogenoalkyl having 1 to 8carbon atoms and 1 to 17 identical or different halogen atoms,halogenoalkenyl or halogenoalkinyl in each case having 2 to 8 carbonatoms and 1 to 15 or 13 identical or different halogen atoms, cyanoalkylhaving 1 to 8 carbon atoms, hydroxyalkyl having 1 to 8 carbon atoms and1 to 6 hydroxyl groups, alkoxyalkyl, alkoxycarbonylalkyl oralkoxycarbonylalkenyl in each case having up to 6 carbon atoms in theindividual alkyl or alkenyl parts, alkylaminoalkyl or dialkylaminoalkylin each case having 1 to 6 carbon atoms in the individual alkyl parts,cycloalkyl having 12 carbon atoms or represents cycloalkyl,cycloalkylalkyl, cycloalkenyl or cycloalkenylalkyl in each case having 3to 8 carbon atoms in the cycloalkyl or cycloalkenyl part and whereappropriate 1 to 6 carbon atoms in the alkyl part, and which are in eachcase optionally monosubstituted or polysubstituted by identical ordifferent substitutents, suitable substituents in each case being:halogen, cyano and also in each case straight-chain or branched alkyl orhalogenoalkyl in each case having 1 to 4 carbon atoms and whereappropriate 1 to 9 identical or different halogen atoms orstraight-chain or branched halogenalkenyl having up to 4 carbon atomsand 1 to 5 halogen atoms or in each case bivalent alkanediyl oralkenediyl in each case having up to 4 carbon atoms; furthermore, R²represents heterocyclylalkyl having 1 to 6 carbon atoms in thestraight-chain or branched alkyl part and 1 to 9 carbon atoms and also 1to 3 hetero atoms--in particular nitrogen, oxygen and/or sulphur--in theheterocyclic part, and which is optionally monosubstituted orpolysubstituted in the heterocyclic part by identical or differentsubstituents, suitable substituents being: halogen, cyano, nitro, andalso in each case straight-chain or branched alkyl, alkoxy, alkylthio,halogenoalkyl, halogenoalkoxy, halogenoalkylthio or alkoxycarbonyl ineach case having 1 to 5 carbon atoms and where appropriate 1 to 9identical or different halogen atoms; furthermore, R² represents in eachcase straight-chain or branched alkoxy having 1 to 8 carbon atoms,alkenyloxy having 2 to 8 carbon atoms or alkinyloxy having 2 to 8 carbonatoms, or, finally, represents aralkyl, aroyl, aryl, aralkyloxy oraryloxy, in each case having 6 to 10 carbon atoms in the aryl part andwhere appropriate 1 to 8 carbon atoms in the straight-chain or branchedalkyl part, and which are in each case optionally monosubstituted orpolysubstituted by identical or different substituents, suitable alkylsubstituents where appropriate being halogen and cyano and suitable arylsubstituents in each case being: halogen, cyano, nitro, hydroxyl, ineach case straight-chain or branched alkyl, alkoxy, alkylthio,halogenoalkyl, halogenoalkoxy, halogenoalkylthio, alkylsulphinyl,alkylsulphonyl, halogenoalkylsulphinyl, halogenoalkylsulphonyl, alkanoylor alkoxycarbonyl in each case having 1 to 6 carbon atoms in the alkylpart and where appropriate 1 to 9 identical or different halogen atoms,cycloalkyl having 3 to 6 carbon atoms and phenoxy, or

R² represents benzyl with a condensed --O--CH₂ --O-- group in the phenylpart,

X represents oxygen or sulphur and

Y represents oxygen or sulphur.

Particularly preferred compounds of the formula (I) are those in which

R¹ represents hydrogen, methyl, ethyl, n- or i-propyl, n-, i-, s- ort-butyl, n- or i-pentyl, n- or i-hexyl, or represents allyl, propargyl,straight-chain or branched halogenoalkyl having 1 to 4 carbon atoms and1 to 9 identical or different halogen atoms, in particular fluorine,chlorine or bromine, or represents methoxymethyl, ethoxymethyl,propoxymethyl, cyclopentyl, cyclohexyl, cyclopropyl, cyclopropylmethyl,cyclohexylmethyl, cyclohexylethyl, or represents tetrahydrofuranyl, orrepresents tetrahydrofuranylmethyl, or represents benzyl or phenyl,which are in each case optionally monosubstituted, disubstituted ortrisubstituted by identical or different substituents, suitablesubstituents being: fluorine, chlorine, bromine, cyano, nitro, methyl,ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy,methylthio, trifluoromethyl, trifluoromethoxy or trifluoromethylthio, R²represents hydrogen, methyl, ethyl, n- or i-propyl, n-, i-, s- ort-butyl, in each case straight-chain or branched pentyl, hexyl, heptyl,optyl, nonyl, decyl or dodecyl, or represents allyl, in each casestraight-chain or branched butenyl, pentenyl or hexenyl, propargyl, ineach case straight-chain or branched butinyl, pentinyl or hexinyl, orrepresents straight-chain or branched halogenoalkyl having 1 to 8 carbonatoms and 1 to 9 identical or different halogen atoms, in particularfluorine, chlorine or bromine, or represents in each case straight-chainor branched halogenoalkenyl or halogenoalkinyl having in each case 3 to8 carbon atoms and 1 to 3 halogen atoms, in particular fluorine orchlorine, or represents in each case straight-chain or branchedcyanolkyl having 1 to 6 carbon atoms in the alkyl part, hydroxyalkylhaving 1 to 6 carbon atoms and 1 to 3 hydroxyl groups, alkoxyalkyl,alkoxycarbonylalkyl or alkoxycarbonylalkenyl, alkylaminoalkyl ordialkylaminoalkyl in each case having up to 4 carbon atoms in theindividual alkyl or alkenyl parts, or represents cyclopropyl,cyclopropylmethyl, cyclopropylethyl, cyclopentyl, cyclohexyl,cycloheptyl, cyclooctyl, cyclohexylmethyl, cyclohexylethyl, cyclohexenylor cyclohexenylmethyl, which are in each case optionallymonosubstituted, disubstituted or trisubstituted by identical ordifferent substituents, suitable substituents in each case being:fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, n-, i-, s-or t-butyl, cyano, methanediyl, ethanediyl, butanediyl, butadienediyl ordichloroallyl;

R² furthermore represents heterocyclylmethyl, heterocyclylpropyl orheterocyclylethyl, which are optionally monosubstituted, disubstitutedor trisubstituted in the heterocyclic part by identical or differntsubstituents, suitable heterocycles in each case being: ##STR9## where Zin each case represents oxygen or sulphur, and where suitablesubstituents in each case are: fluorine, chlorine, bromine, cyano,nitro, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy,ethoxy, methylthio, trifluoromethyl, trifluoromethoxy ortrifluoromethylthio;

R² furthermore represents in each case straight-chain or branched alkoxyhaving 1 to 6 carbon atoms, alkenyloxy having 3 to 6 carbon atoms oralkinyloxy having 3 to 6 carbon atoms, or represents optionallystraight-chain or branched benzyl, phenylethyl, phenylpropyl,phenylbutyl, phenylpentyl, phenylhexyl, phenylheptyl, phenylcyanomethyl,phenylcyanoethyl, phenylcyanopropyl, benzyloxy, phenylethyloxy, phenoxy,benzoyl, phenyl or naphthyl, which are in each case optionallymonosubstituted, disubstituted or trisubstituted by identical ordifferent substituents, suitable phenyl substituents in each case being:fluorine, chlorine, bromine, hydroxyl, cyano, nitro, methyl, ethyl, n-or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, methylthio,trifluoromethyl, trifluoromethoxy, trifluoromethylthio,trifluoromethylsulphinyl, trifluoromethylsulphonyl, methylsulphinyl,methylsulphonyl, acetyl, propionyl, methoxycarbonyl, ethoxycarbonyl,cyclohexyl or phenoxy,

X represents oxygen or sulphur and

Y represents oxygen or sulphur.

Very particularly preferred compounds of the formula (I) are those inwhich

R¹ represents hydrogen, methyl, ethyl, n- or i-propyl, methoxymethyl,ethoxymethyl or propoxymethyl,

R² represents hydrogen, or represents methyl, ethyl, n- or i-propyl, n-,i-, s- or t-butyl, allyl, propargyl, in each case straight-chain orbranched pentyl, hexyl, heptyl, octyl, butenyl, pentenyl, hexenyl,butinyl, pentinyl or hexinyl each of which is optionallymonosubstituted, disubstituted or trisubstituted by halogen; oradditionally represents cyclopropyl, cyclopentyl, cyclohexyl,cyclohexenyl, cyclopropylmethyl, cyclopropylethyl, cyclohexylmethyl,cyclohexylethyl or cycloheptyl which are in each case optionallymonosubstituted, disubstituted or trisubstituted by identical ordifferent substituents from the group comprising fluorine, chlorine,methyl, ethyl and/or cyano; and finally represents benzyl, phenylethylor phenyl,

X represents oxygen or sulphur and

Y represents oxygen or sulphur.

Especially noteworthy are those compounds in which R¹ representsn-propyl, 1-propyl, n-butyl, i-butyl, s-butyl, t-butyl or cyclopropyl,or especially i-propyl, s-butyl or cyclopropyl, and X and Y representoxygen.

The following substituted triazolinones of the general formula (I)##STR10## may be mentioned individually in addition to the compoundsmentioned in the preparation examples:

    ______________________________________                                        R.sup.1   R.sup.2               X      Y                                      ______________________________________                                        CH.sub.3                                                                                 ##STR11##            O      O                                      CH.sub.3                                                                                 ##STR12##            O      O                                      CH.sub.3                                                                                 ##STR13##            O      O                                      CH.sub.3  C(CH.sub.3).sub.3     O      S                                      CH.sub.3  C(CH.sub.3).sub.3     S      S                                      CH.sub.3                                                                                 ##STR14##            S      S                                      CH.sub.3                                                                                 ##STR15##            O      O                                      C.sub.2 H.sub.5                                                                         C(CH.sub.3).sub.3     O      O                                      C.sub.2 H.sub.5                                                                         C(CH.sub.3).sub.3     O      S                                      C.sub.2 H.sub.5                                                                         C(CH.sub.3).sub.3     S      O                                      C.sub.2 H.sub.5                                                                          ##STR16##            O      S                                      C.sub.2 H.sub.5                                                                          ##STR17##            S      O                                      C.sub.2 H.sub.5                                                                          ##STR18##            O      O                                      C.sub.2 H.sub.5                                                                          ##STR19##            O      S                                      C.sub.2 H.sub.5                                                                          ##STR20##            S      O                                      C.sub.2 H.sub.5                                                                          ##STR21##            O      O                                      H         C(CH.sub.3).sub.3     O      O                                                 ##STR22##            O      O                                      H                                                                                        ##STR23##            O      O                                      H         C(CH.sub.3).sub.3     O      S                                      H         C(CH.sub.3).sub.3     S      O                                      H                                                                                        ##STR24##            O      S                                      H                                                                                        ##STR25##            S      O                                      CH.sub.3                                                                                 ##STR26##            O      O                                      CH.sub.3                                                                                 ##STR27##            O      O                                      CH.sub.3                                                                                 ##STR28##            O      O                                      CH.sub.3                                                                                 ##STR29##            O      O                                      CH.sub.3                                                                                 ##STR30##            O      O                                      CH.sub.3                                                                                 ##STR31##            O      O                                      CH.sub.3                                                                                 ##STR32##            O      O                                      CH.sub.3                                                                                 ##STR33##            O      O                                      CH.sub.3                                                                                 ##STR34##            O      O                                      CH.sub.3                                                                                 ##STR35##            O      O                                      CH.sub.3                                                                                 ##STR36##            O      O                                      CH.sub.3                                                                                 ##STR37##            O      O                                      CH.sub.3                                                                                 ##STR38##            O      O                                      CH.sub.3                                                                                 ##STR39##            O      O                                      CH.sub.3                                                                                 ##STR40##            O      O                                      CH.sub.3                                                                                 ##STR41##            O      O                                      CH.sub.3                                                                                 ##STR42##            O      O                                      CH.sub.3                                                                                 ##STR43##            O      O                                      CH.sub.3                                                                                 ##STR44##            O      O                                      CH.sub.3                                                                                 ##STR45##            O      O                                      CH.sub.3                                                                                 ##STR46##            O      O                                      CH.sub.3                                                                                 ##STR47##            O      O                                      CH.sub.3                                                                                 ##STR48##            O      O                                      CH.sub.3                                                                                 ##STR49##            O      O                                      CH.sub.3                                                                                 ##STR50##            O      O                                      CH.sub.3                                                                                 ##STR51##            O      O                                      CH.sub.3                                                                                 ##STR52##            O      O                                      CH.sub.3                                                                                 ##STR53##            O      O                                      CH.sub.3                                                                                 ##STR54##            O      O                                      CH.sub.3                                                                                 ##STR55##            O      O                                      CH.sub.3                                                                                 ##STR56##            O      O                                      CH.sub.3                                                                                 ##STR57##            O      O                                      CH.sub.3                                                                                 ##STR58##            O      O                                      CH.sub.3                                                                                 ##STR59##            O      O                                      CH.sub.3                                                                                 ##STR60##            O      O                                      CH.sub.3                                                                                 ##STR61##            O      O                                      CH.sub.3                                                                                 ##STR62##            O      S                                      CH.sub.3                                                                                 ##STR63##            O      S                                      -CH.sub.3                                                                                ##STR64##            O      S                                      CH.sub.3                                                                                 ##STR65##            O      S                                      CH.sub.3                                                                                 ##STR66##            O      S                                      CH.sub.3  (CH.sub.2).sub.2CH.sub.3                                                                            O      S                                      CH.sub.3                                                                                 ##STR67##            O      S                                      CH.sub.3                                                                                 ##STR68##            O      S                                      CH.sub.3                                                                                 ##STR69##            O      S                                      CH.sub.3                                                                                 ##STR70##            O      S                                      CH.sub.3                                                                                 ##STR71##            O      S                                      CH.sub.3  (CH.sub.2).sub.2CH.sub.3                                                                            S      O                                      CH.sub.3  (CH.sub.2).sub.3CH.sub.3                                                                            S      O                                      CH.sub.3                                                                                 ##STR72##            S      O                                      CH.sub.3                                                                                 ##STR73##            S      O                                      (CH.sub.3).sub.2 CH                                                                      ##STR74##            O      O                                      (CH.sub.3).sub.2 CH                                                                      ##STR75##            O      O                                      (CH.sub.3).sub.2 CH                                                                      ##STR76##            O      O                                      (CH.sub.3).sub.2 CH                                                                      ##STR77##            O      O                                      (CH.sub.3).sub.2 CH                                                                      ##STR78##            O      O                                      (CH.sub.3).sub.2 CH                                                                      ##STR79##            O      O                                      (CH.sub.3).sub.2 CH                                                                      ##STR80##            O      O                                      (CH.sub.3).sub.2 CH                                                                      ##STR81##            O      O                                      (CH.sub.3).sub.2 CH                                                                      ##STR82##            O      O                                      (CH.sub.3).sub.2 CH                                                                      ##STR83##            O      O                                      (CH.sub. 3).sub.2 CH                                                                     ##STR84##            O      O                                      (CH.sub.3).sub.2 CH                                                                      ##STR85##            O      O                                      (CH.sub.3).sub.2 CH                                                                      ##STR86##            O      O                                      (CH.sub.3).sub.2 CH                                                                      ##STR87##            O      O                                      (CH.sub.3).sub.2 CH                                                                      ##STR88##            O      O                                      (CH.sub.3).sub.2 CH                                                                      ##STR89##            O      O                                      (CH.sub.3).sub.2 CH                                                                      ##STR90##            O      O                                      (CH.sub.3).sub.2 CH                                                                      ##STR91##            O      O                                      (CH.sub.3).sub.2 CH                                                                      ##STR92##            O      O                                      (CH.sub.3).sub.2 CH                                                                      ##STR93##            O      O                                      (CH.sub.3).sub.2 CH                                                                      ##STR94##            O      O                                      (CH.sub.3).sub.2 CH                                                                      ##STR95##            O      O                                      (CH.sub.3).sub.2 CH                                                                     (CH.sub.2).sub.2CH.sub.3                                                                            O      O                                      (CH.sub.3).sub.2 CH                                                                     (CH.sub.2).sub.3CH.sub.3                                                                            O      O                                      (CH.sub.3).sub.2 CH                                                                     CH(CH.sub.3).sub.2    O      O                                      (CH.sub.3).sub.2 CH                                                                      ##STR96##            O      O                                      (CH.sub.3).sub.2 CH                                                                      ##STR97##            O      O                                      (CH.sub.3).sub.2 CH                                                                      ##STR98##            O      O                                      (CH.sub.3).sub.2 CH                                                                      ##STR99##            O      O                                      (CH.sub.3).sub.2 CH                                                                      ##STR100##           O      O                                      (CH.sub.3).sub.2 CH                                                                      ##STR101##           O      O                                      (CH.sub.3).sub.2 CH                                                                      ##STR102##           O      O                                      (CH.sub.3).sub.2 CH                                                                      ##STR103##           O      O                                      (CH.sub.3).sub.2 CH                                                                      ##STR104##           O      O                                      (CH.sub.3).sub.2 CH                                                                     C(CH.sub.3).sub.3     O      O                                       ##STR105##                                                                              ##STR106##           O      O                                       ##STR107##                                                                              ##STR108##           O      O                                       ##STR109##                                                                              ##STR110##           O      O                                       ##STR111##                                                                              ##STR112##           O      O                                       ##STR113##                                                                              ##STR114##           O      O                                       ##STR115##                                                                              ##STR116##           O      O                                       ##STR117##                                                                              ##STR118##           O      O                                       ##STR119##                                                                              ##STR120##           O      O                                       ##STR121##                                                                              ##STR122##           O      O                                       ##STR123##                                                                              ##STR124##           O      O                                       ##STR125##                                                                              ##STR126##           O      O                                       ##STR127##                                                                              ##STR128##           O      O                                       ##STR129##                                                                              ##STR130##           O      O                                       ##STR131##                                                                              ##STR132##           O      O                                       ##STR133##                                                                              ##STR134##           O      O                                       ##STR135##                                                                              ##STR136##           O      O                                       ##STR137##                                                                              ##STR138##           O      O                                       ##STR139##                                                                              ##STR140##           O      O                                       ##STR141##                                                                              ##STR142##           O      O                                       ##STR143##                                                                              ##STR144##           O      O                                       ##STR145##                                                                              ##STR146##           O      O                                       ##STR147##                                                                              ##STR148##           O      O                                       ##STR149##                                                                             (CH.sub.2).sub.2CH.sub.3                                                                            O      O                                       ##STR150##                                                                             (CH.sub.2).sub.3CH.sub.3                                                                            O      O                                       ##STR151##                                                                             CH(CH.sub.3).sub.2    O      O                                       ##STR152##                                                                              ##STR153##           O      O                                       ##STR154##                                                                              ##STR155##           O      O                                       ##STR156##                                                                              ##STR157##           O      O                                       ##STR158##                                                                              ##STR159##           O      O                                       ##STR160##                                                                              ##STR161##           O      O                                       ##STR162##                                                                              ##STR163##           O      O                                       ##STR164##                                                                              ##STR165##           O      O                                       ##STR166##                                                                              ##STR167##           O      O                                       ##STR168##                                                                              ##STR169##           O      O                                       ##STR170##                                                                             C(CH.sub.3).sub.3     O      O                                       ##STR171##                                                                              ##STR172##           O      O                                       ##STR173##                                                                              ##STR174##           O      O                                       ##STR175##                                                                              ##STR176##           O      O                                       ##STR177##                                                                              ##STR178##           O      O                                       ##STR179##                                                                              ##STR180##           O      O                                       ##STR181##                                                                              ##STR182##           O      O                                       ##STR183##                                                                              ##STR184##           O      O                                       ##STR185##                                                                              ##STR186##           O      O                                       ##STR187##                                                                              ##STR188##           O      O                                       ##STR189##                                                                              ##STR190##           O      O                                       ##STR191##                                                                              ##STR192##           O      O                                       ##STR193##                                                                              ##STR194##           O      O                                       ##STR195##                                                                              ##STR196##           O      O                                       ##STR197##                                                                              ##STR198##           O      O                                       ##STR199##                                                                              ##STR200##           O      O                                       ##STR201##                                                                              ##STR202##           O      O                                       ##STR203##                                                                              ##STR204##           O      O                                       ##STR205##                                                                              ##STR206##           O      O                                       ##STR207##                                                                              ##STR208##           O      O                                       ##STR209##                                                                              ##STR210##           O      O                                       ##STR211##                                                                              ##STR212##           O      O                                       ##STR213##                                                                              ##STR214##           O      O                                       ##STR215##                                                                             (CH.sub.2).sub.2CH.sub.3                                                                            O      O                                       ##STR216##                                                                             (CH.sub.2).sub.3CH.sub.3                                                                            O      O                                       ##STR217##                                                                             CH(CH.sub.3).sub.2    O      O                                       ##STR218##                                                                              ##STR219##           O      O                                       ##STR220##                                                                              ##STR221##           O      O                                       ##STR222##                                                                              ##STR223##           O      O                                       ##STR224##                                                                              ##STR225##           O      O                                       ##STR226##                                                                              ##STR227##           O      O                                       ##STR228##                                                                              ##STR229##           O      O                                       ##STR230##                                                                              ##STR231##           O      O                                       ##STR232##                                                                              ##STR233##           O      O                                       ##STR234##                                                                              ##STR235##           O      O                                       ##STR236##                                                                             C(CH.sub.3).sub.3     O      O                                      ______________________________________                                    

If, for example,1-(N-isobutylcarbamoyl)-4-isopropylideneimino-3-methyl-1,2,4-triazolin-5-oneis used as the starting compound, then the course of the reaction of theprocess (a) according to the invention can be represented by thefollowing equation: ##STR237## If, for example,4-amino-3-cyclopropyl-1,2,4-(1H)-triazolin-5-one and t-butyl isocyanateare used as the starting substances, the course of the reaction ofprocess (b) according to the invention may be represented by thefollowing equation: ##STR238## If, for example,1-phenoxycarbonyl-4-amino-3-s-butyl-1,2,4-triazolin-5-one andN,N-diethylpropane-1,3-diamine are used as starting substances thecourse of the reaction of process (c) according to the invention may berepresented by the following equation: ##STR239## If, for example,4-amino-3-isopropyl-1,2,4-(1H)-triazolin-5-one and N-isopropylphenylcarbamate are used as the starting substances, the course of thereaction of process (d) according to the invention may be represented bythe following equation: ##STR240##

The hydrazones of the formula (II) were hitherto unknown. They are alsosubject matter of the present invention. However, they are obtainedanalogously to known processes (compare, for example, Acta Pol. Pharm.38, 153-162 [1981] or C.A. 95: 203841j), for example when1-unsubstituted 4-amino-triazolinones of the formula (III) ##STR241## inwhich R¹ and X have the abovementioned meaning, are reacted withaldehydes or ketones of the formula (VII) ##STR242## in which R³ and R⁴have the abovementioned meaning, if appropriate in the presence of adiluent such as, for example, dichloromethane or toluene, and ifappropriate in the presence of a catalyst such as, for example,p-toluenesulphonic acid, at temperatures between 40° C. and 120° C., andthe 1-unsubstituted triazolinone-hydrazones of the formula (VIII)##STR243## in which R¹, R³, R⁴ and X have the abovementioned meaning,thus obtainable are reacted in a subsequent 2nd step withiso(thio)cyanates of the formula (IV)

    R.sup.2 --N═C═Y                                    (IV)

in which R² and Y have the abovementioned meaning, if appropriate in thepresence of a diluent such as, for example, dichloromethane or dioxane,and if appropriate in the presence of a reaction auxiliary such as, forexample, triethylamine, at temperatures between 50° C. and 150° C., oralternatively are reacted in a subsequent 2nd step with(thio)chloroformic acid esters of the formula ##STR244## in which R⁵represents alkyl, aryl or arylalkyl and

Y has the abovementioned meaning,

if appropriate, in the presence of a diluent such as for exampletetrahydrofuran and, if appropriate, in the presence of a reactionauxiliary such as for example sodium hydride or potassium-t-butylate attemperatures between -20° C. and +40° C. and the resulting triazolinonesof the formula (X), ##STR245## in which R¹, R³, R⁴, R⁵, X and Y have theabovementioned meaning, are reacted in a subsequent 3rd step with aminesof the formula (VI),

    R.sup.2 --NH.sub.2                                         (VI)

in which R² has the abovementioned meaning, if appropriate, in thepresence of a diluent such as for example tetrahydrofuran and, ifappropriate, in the presence of a base, such as for example sodiumhydroxide, potassium hydroxide or diazabicycloundecane (DBU), attemperatures between 20° C. and 50° C.

Some of the 1-unsubstituted 4-amino-triazolinones of the formula (III)are known and can be obtained in analogy to known processes (cf., forexample, J. Heterocycl. Chem. 16, 403 [1979]; J. Heterocycl. Chem. 17,1691 [1980]; Europ. J. Med. Chem. 18, 215 [1983]; Chem. Ber. 98, 3025[1965]; Liebigs Ann. Chem. 637, 135 [1960]; J. Heterocycl. Chem. 21,1769-1774 [1984]; Chim. Acta Turc. 7, 269-290 [1979] or CA 106 (17):138338e [1986]).

The aldehydes or ketones of the formula (VII) are generally knowncompounds of organic chemistry.

If, for example, 1-ethoxycarbonyl-4-amino-3-methyl-1,2,4-triazolin-5-oneand N,N-diethylpropane-1,3-diamine are used as starting compounds, thenthe course of the reaction of the process (c) can be represented by thefollowing equation: ##STR246##

Formula (II) provides a general definition of the hydrazones required asstarting materials for carrying out the process (a) according to theinvention. In this formula (II), R¹, R², X and Y preferably representthose radicals which have already been mentioned as preferred for thesesubstituents in connection with the description of the substancesaccording to the invention, of the formula (I).

R³ and R⁴ in each case independently of one another preferably representhydrogen, or represent straight-chain or branched alkyl having 1 to 4carbon atoms, or represent phenyl or benzyl.

The majority of the 1-unsubstituted triazolinone hydrazones of theformula (VIII) are known (cf., for example, J. Heterocycl. Chem. 20,77-80 [1983]; J. Heterocycl. Chem. 16 403-407 [1979]; Chim. Acta. Turc.7, 269-290 [1979]; J. chem. Soc.; Perkin Trans. II, 1973, 9-11; J. org.Chem. 36, 2190-2192 [1971]).

The (thio)chloroformic acid esters of the formula (IX) are generallyknown compounds of organic chemistry.

Some of the triazolinones of the formula (X) mentioned as intermediatesare known (cf. for example Acta. Pol. Pharm. 38, 153-162 [1981] or C.A.95: 203841j).

Triazolinones of the formula (Xa), ##STR247## in which R¹⁻⁻¹ representsalkyl and

R³, R⁴, R⁵, X and Y have the abovementioned meaning,

are not yet known and are also a subject of the present application.

R¹⁻⁻¹ preferably represents straight-chain or branched alkyl with 1 to4, in particular with 1 to 3 carbon atoms; R¹⁻⁻¹ particularly preferablyrepresents methyl,

R³ and R⁴ preferably, in each case independently of one anotherrepresent hydrogen, straight-chain or branched alkyl with 1 to 4 carbonatoms or phenyl or benzyl,

R⁵ preferably represents straight-chain or branched alkyl with 1 to 4carbon atoms for benzyl or phenyl, optionally mono- to trisubstituted byidentical or different substituents, the following being possiblesubstituents in each case: halogen, cyano, nitro, alkyl, alkoxy oralkylthio, each of which has 1 to 4 carbon atoms and each of which isstraight-chain or branched, or halogenoalkyl, halogenoalkoxy orhalogenoalkylthio, each of which has 1 to 4 carbon atoms and 1 to 9identical or different halogen atoms and each of which is straight-chainor branched;

R⁵ represents in particular methyl, ethyl, n- or i-propyl, n-, i-, s- ort-butyl, or benzyl or phenyl, optionally mono- to disubstituted byidentical or different substituents, the following being possiblesubstituents in each case: fluorine, chlorine, bromine, cyano, nitro,methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy,n- or i-propoxy, methylthio, trifluoromethyl, trifluoromethoxy ortrifluoromethylthio;

X and Y in each case independently of one another represent oxygen andsulphur, preferably oxygen. The 1H-triazolinones required as startingmaterials for carrying out the process (b) according to the inventionare defined generally by the formula (III).

In this formula (III) R¹ and Z preferably represent those radicals whichwere already mentioned as preferred substituents in connection with thedescription of the compounds of the formula (I) according to theinvention.

The 1H-triazolinones of the formula (III) are either known, or they canbe obtained in analogy to known processes (cf., for example, B.J.Heterocycl. Chem. 16, 403 [1979]. J. Heterocycl. Chem. 17, 1691 [1980];Europ. J. med. Chem. 18, 215 [1983]; Chem. Ber. 98, 3025 [1965]; LiebigsAnn. Chem. 637, 135 [1960]; J. Heterocycl. Chem. 21, 1769-1774 [1984];Chim. Acta. Turc. 7, 269-270 [1979]; CA 106 (17): 138338e [1986]).

1-Unsubstituted 4-aminotriazolinones of the formula (IIIa) ##STR248## inwhich R¹⁻⁻¹ represents n-butyl, i-butyl, s-butyl or cyclopropyl, inparticular represents s-butyl or cyclopropyl, were hitherto unknown andare also the subject-matter of the invention.

They are obtained in analogy to known processes (cf., for example, J.Heterocycl. Chem. 21, 1769 [1984], and Chem. Ber. 98, 3025 [1965]), forexample when hydrazine hydrate is reacted with diphenyl carbonate in acustomary manner, and the resulting carbonic acid hydrazide is cyclized,likewise in a customary manner, with carboxylic acid derivatives of theformula (XII)

    R.sup.1--1 --COOR.sup.6                                    (XII)

in which

R¹⁻⁻¹ has the abovementioned meaning and

R⁶ represents hydrogen, or represents straight-chain or branched alkylhaving 1 to 4 carbon atoms,

at temperatures between 150° C. and 250° C. (cf. also the preparationexamples).

Carboxylic acid derivatives of the formula (XII) are generally knowncompounds of organic chemistry.

The iso(thio)cyanates also required as starting materials for carryingout the process (b) according to the invention are defined generally bythe formula (IV). In this formula (IV) R² and Y preferably representthose radicals which have already been mentioned as preferredsubstituents in connection with the description of the compounds of theformula (I) according to the invention.

The iso(thio)cyanates of the formula (IV) are mostly known compounds oforganic chemistry. The compounds 2,2,2-trifluoroisopropylcyanate and2,2,2-trifluoro-1,1-dimethyl-ethylcyanate are not yet known but canhowever be prepared according to known methods.

Iso(thio)cyanates can be obtained, for example, when correspondingamines are reacted with phosgene, if appropriate, in the presence of abase such as, for example, triethylamine (compare e.g. DE-OS2, 804,802,DE-OS 2,512,514, U.S. Pat. Nos. 3,584,028, 2,706,753, 3,311,654, JA50/29,599, Synthesis 1985, page 682 or J. Am. Chem. Soc. 77, 1901-1902(1955)).

The triazolinones required as starting materials for carrying out theprocess (c) according to the invention are defined generally by theformula (V). In this formula (V), R¹, X and Y preferably represent thoseradicals which have already been mentioned as preferred substituents inconnection with the description of the compounds of the formula (I)according to the invention.

R⁵ preferably represent straight-chain or branched alkyl with 1 to 4carbon atoms or benzyl or phenyl, optionally mono- to trisubstituted byidentical or different substituents, the following being possiblesubstituents in each case: halogen, cyano, nitro, alkyl, alkoxy oralkylthio, each of which has 1 to 4 carbon atoms and each of which isstraight-chain or branched, or halogenoalkyl, halogenoalkoxy orhalogenoalkylthio, each of which has 1 to 4 carbon atoms and 1 to 9identical or different halogen atoms and each of which is straight-chainor branched;

R⁵ represents in particular methyl, ethyl, n- or i-propyl, n-, i-, s- ort-butyl or benzyl or phenyl, optionally mono- to disubstituted byidentical or different substituents, possible substituents in each casebeing: fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, n- ori-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy,methylthio, trifluoromethyl, trifluoromethoxy or trifluoromethylthio.Some of the triazolinones of the formula (V) are known (cf. for exampleJ. Heterocycl. Chem. 17, 1691-1696 [1980]).

Triazolinones of the formula (Va) ##STR249## in which R¹⁻⁻¹ representsalkyl, preferably straight-chain or branched alkyl with 1 to 4, inparticular with 1 to 3 carbon atoms, and particularly preferably methyland

R⁵, X and Y have the abovementioned meaning,

are not yet known and are also a subject of the present application.

They are obtained analogously to the preparation of the known compoundsof the formula (V), by reacting 1H-triazolinones of the formula (IIIa)##STR250## in which R¹⁻⁻¹ and X have the abovementioned meaning, with(thio)chloroformic acid esters of the formula (IX), ##STR251## in whichR⁵ and Y have the abovementioned meaning, if appropriate in the presenceof a diluent such as for example tetrahydrofuran and if appropriate inthe presence of a reaction auxiliary such as for examplepotassium-t-butylate or sodium hydride at temperatures between -20° C.and +40° C. (cf, also the preparation examples).

The 1H-triazolinones of the formula (IIIa) are known or can be obtainedanalogously to known processes (cf. for example J. Heterocycl. Chem. 16,403 [1979]; J. Heterocycl. Chem. 17, 1691 [1980]; Europ. J. med. Chem.18, 215 [1983]; Chem. Ber. 98, 3025 [1965]; Liebigs Ann. Chem. 637, 135[1960]).

Formula (VII) provides a general definition of the urethanes furthermorerequired as starting substances for carrying out process (d) accordingto the invention. In this formula (VII), R² preferably represents thoseradicals which have already been mentioned in connection with thedescription of the substances of the formula (I) according to theinvention as being preferred for these substituents. R⁵ preferablyrepresents those radicals which have already been mentioned inconnection with the description of the precursors of the formula (V) asbeing preferred, or particularly preferred, for this substituent.

The urethanes of the formula (VII) are generally known compounds oforganic chemistry, or they can be obtained with the aid of generallyknown processes.

All inorganic and organic acids customarily utilizable for hydrazonecleavage are suitable as acids for carrying out the process (a)according to the invention. Inorganic mineral acids such as hydrochloricacid, sulphuric acid or phosphoric acid are preferably used.

All customary organic or inorganic solvents are suitable as diluents forcarrying out the process (a) according to the invention. Polar organicsolvents miscible with water, in particular alcohols, such as methanol,ethanol, propanol or butanol, their mixtures with water or pure waterare preferably used as diluents.

The reaction temperatures can be varied within a relatively wide rangein carrying out the process (a) according to the invention. In general,the reaction is carried out at temperatures between 20° C. and 150° C.,preferably at temperatures between 50° C. and 120° C.

The process (a) according to the invention is customarily carried out atatmospheric pressure or under reduced pressure. If the process iscarried out under reduced pressure, then suitable pressure ranges arebetween 20 and 400 mbar, preferably between 100 and 200 mbar.

For carrying out the process (a) according to the invention, 1 to 50mols, preferably 1 to 20 mols, of acid are generally employed per moleof hydrazone of the formula (II). To achieve this, the hydrazone of theformula (II) is dissolved in a suitable amount of diluent, then thenecessary amount of acid is added and the mixture is slowly concentratedunder reduced pressure over several hours.

In a particular embodiment it is also possible to carry out the process(a) according to the invention and the preparation of the precursors ofthe formula (II) necessary for said process in one reaction step, in aso-called one-pot process.

For this purpose it is possible to select the triazolinones of theformula (X) as starting compounds and to react them successively, in aone-pot process, with amines of the formula (VI) and then with acidaccording to process (a) according to the invention (in this connectioncf. also the preparation examples), or alternatively, to select thetriazoline hydrazones of the formula (VIII) as starting compounds and toreact them successively, in a one-pot process with (thio)chloroformicacid esters of the formula (IX), then with amines of the formula (VI)and then with acid according to process (a) according to the invention.

Inert organic solvents can be used as dilents for carrying out process(b) according to the invention. These include in particular aliphatic,alicyclic or aromatic, optionally halogenated hydrocarbons, such as forexample benzine, benzene, toluene, xylene, chlorobenzene, petroleumether, hexane, cyclohexane, dichloromethane, chloroform, carbontetrachloride, ethers, such as diethyl ether, dioxane, tetrahydrofuranor ethylene glycol dimethyl or diethyl ether, nitriles, such asacetonitrile or propionitrile, amides, such as dimethylformamide,dimethyl acetamide, N-methylformamide, N-methylpyrrolidone orhexamethylphosphoric acid triamide or esters, such as ethyl acetate.

The process (b) according to the invention is optionally carried out inthe presence of a suitable reaction auxiliary. All customary inorganicor organic bases can be used as reaction auxiliaries. They include forexample tertiary amines, such as triethylamine, N,N-dimethylaniline,N,N-diethylbenzylamine, N,N-dimethylcyclohexylamine or dibutyl tindilaureate, pyridine, N,N-dimethylaminopyridine, diazabicyclooctane(DABCO), diazabicyclononene (DBN) and diazabicycloundecane (DBU).

When carrying out the process (b) according to the invention thereaction temperatures can be varied within a relatively large range. Ingeneral temperatures between 0° C. and 150° C., and preferablytemperatures between 20° C. and 100° C. are used.

In general 1.0 to 2.0 mols, preferably 1.0 to 1.5 mols, ofiso(thio)cyanate of the formula (IV) and, where appropriate, 0.001 to2.0 mols, preferably 0.001 to 1.0 mol, of reaction auxiliaries are usedper mol of 1H-triazolinone of the formula (III), for carrying outprocess (b) according to the invention.

The reaction, the working up and the isolation of the reaction productsare carried out according to generally auxiliary methods.

Inert organic solvents can be used as diluents for carrying out theprocess (c) according to the invention. These include in particularaliphatic, alicyclic or aromatic, optionally halogenated hydrocarbonssuch as for example benzine, benzene, toluene, xylene, chlorobenzene,petroleum ether, hexane, cyclohexane, dichloromethane, chloroform,carbon tetrachloride, ethers, such as diethyl ether, dioxane,tetrahydrofuran or ethylene glycol dimethyl or diethyl ether, nitriles,such as acetonitrile or propionitrile, amides, such as dimethylformamide, dimethyl acetamide, N-methylformanilide, N-methylpyrrolidoneor hexamethylphosphoric acid triamide or esters, such as ethyl acetate,or sulphoxides, such as dimethyl sulphoxide.

The processes (c) and (d) according to the invention can optionally becarried out in the presence of a suitable reaction auxiliary. Allcustomary inorganic or organic bases are suitable as reactionauxiliaries. They include for example alkali metal hydroxides, such assodium hydroxide or potassium hydroxide, alkali metal carbonates, suchas sodium carbonate, potassium carbonate or sodium hydrogencarbonate,and tertiary amines, such as triethylamine, N,N-dimethylaniline,pyridine, N,N-dimethylaminopyridine, diazabicyclooctane (DABCO),diazabicyclononene (DBN) or diazabicycloundecane (DBU).

When carrying out processes (C) and (d) according to the invention thereaction temperatures can be varied within a relatively large range. Ingeneral temperatures between 0° C. and 120° C. and preferablytemperatures between 20° C. and 50° C. are used.

For carrying out process (c) according to the invention, 1.0 to 5.0moles, preferably 1.0 to 2.5 moles, of amine of the formula (VI) and ifappropriate 1.0 to 2.0 moles, preferably 1.0 to 1.2 moles, of reactionauxiliary are generally employed per mole of triazolinone of the formula(V). The reaction is carried out and the reaction products are worked upand isolated by generally customary methods.

In a special embodiment of the procedure, it is also possible to carryout process (c) according to the invention and to prepare the precursorsof the formula (V) required for this, in one reaction step in aso-called one-pot process.

In this way of carrying out the reaction, the starting materials are1H-triazolinones of the formula (III), which are reacted in successionin a one-pot process, initially with chloroformic acid esters of theformula (X) and subsequently with amines of the formula (VI), inaccordance with process (c) according to the invention.

For carrying out process (d) according to the invention, 1.0 to 5.0moles, preferably 1.0 to 2.5 moles, of urethane of the formula (VII)and, if appropriate, 1.0 to 5.0 moles, preferably 1.0 to 2.5 moles, ofreaction auxiliary are generally employed per mole of 1H-triazolinone ofthe formula (III). The reaction is carried out and the reaction productsare worked up and isolated by generally customary methods.

Another method to obtain compounds of the formula (I) according to theinvention comprises reacting oxadiazolinones of the formula (XI),##STR252## in which R¹, R² and Y have the abovementioned meaning, withhydrazine hydrate in the presence of a suitable diluent such as forexample methanol or ethanol at temperatures between 20° C. and 100° C.and thermally cyclizing the resulting carbazidic acid derivatives of theformula (XII) ##STR253## in which R¹, R² and Y have the abovementionedmeaning, in the presence of a suitable diluent such as for exampletoluene, chlorobenzene or dichlorobenzene, at temperatures between 80°C. and 200° C.

Oxadiazolinones of the formula (XI) are known (cf. for example FR 14 15605 or C.A. 64: P5105 g and NL 6 510 645 or C.A. 65: P2274d-f) or can beobtained by generally known processes, for example by reacting thecorresponding 4H-oxadiazolinones with iso(thio)cyanates of the formula(IV) by a procedure analogous to that used for carrying out the process(b) according to the invention or to that used for synthesizing theprecursors of the formula (II).

The purification of the final products of the formula (I) is carried outwith the aid of customary processes, for example by columnchromatography or by recrystallization. The characterization is carriedout with the aid of the melting point or with the aid of the protonnuclear magnetic resonance spectrum in the case of non-crystallizablecompounds.

The active compounds according to the invention can be used asdefoliants, desiccants, agents for destroying broad-leaved plants and,especially, as weed-killers. By weeds, in the broadest sense, there areto be understood all plants which grow in locations where they areundesired. Whether the substances according to the invention act astotal or selective herbicides depends essentially on the amount used.

The active compounds according to the invention can be used, forexample, in connection with the following plants:

Dicotyledon weeds of the genera: Sinapis, Lepidium, Galium, Stellaria,Matricaria, Anthemis, Galinsoga, Chenopodium, Urtica, Senecio,Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum,Sesbania, Ambrosia, Cirsium, Carduus, Sonchus, Solanum, Rorippa, Rotala,Lindernia, Lamium, Veronica, Abutilon, Emex, Datura, Viola, Galeopsis,Papaver, Centaurea and Mercurialis.

Dicotyledon cultures of the genera: Gossypium, Glycine, Beta, Daucus,Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana,Lycopersicon, Arachis, Brassica, Lactuca, Cucumis and Cucurbita.

Monocotyledon weeds of the genera: Echinochloa, Setaria, Panicum,Digitaria, Phleum, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus,Avena, Cyperus, Sorghum, Agropyron, Cynodon, Monochoria, Fimbristylis,Sagittaria, Eleocharis, Scirpus, Paspalum, Ischaemum, Sphenoclea,Dactyloctenium, Agrostis, Alopecurus and Apera.

Monocotyledon cultures of the genera: Oryza, Zea, Triticum, Hordeum,Avena, Secale, Sorghum, Panicum, Saccharum, Ananas, Asparagus andAllium.

However, the use of the active compounds according to the invention isin no way restricted to these genera, but also extends in the samemanner to other plants.

The compounds are suitable, depending on the concentration, for thetotal combating of weeds, for example on industrial terrain and railtracks, and on paths and squares with or without tree plantings.Equally, the compounds can be employed for combating weeds in perennialcultures, for example afforestations, decorative tree plantings,orchards, vineyards, citrus groves, nut orchards, banana plantations,coffee plantations, tea plantations, rubber plantations, oil palmplantations, cocoa plantations, soft fruit plantings and hopfields, andfor the selective combating of weeds in annual cultures.

In this way the active compounds according to the invention can be usedwith particularly good effect for combating monocotyledon anddicotyledon weeds, in particular in dicotyledon cultures, such as forexample sugarbeets, corn, wheat and barley.

In particular, the outstanding activity against mercury (Mercurialis), aproblem weed which is difficult to control, is worthy of mention.

The active compounds can be converted to the customary formulations,such as solutions, emulsions, wettable powders, suspensions, powders,dusting agents, pastes, soluble powders, granules, suspension-emulsionconcentrates, natural and synthetic materials impregnated with activecompound, and very fine capsules in polymeric substances.

These formulations are produced in known manner, for example by mixingthe active compounds with extenders, that is liquid solvents and/orsolid carriers, optionally with the use of surface-active agents, thatis emulsifying agents and/or dispersing agents and/or foam-formingagents.

In the case of the use of water as an extender, organic solvents can,for example, also be used as auxiliary solvents. As liquid solvents,there are suitable in the main: aromatics, such as xylene, toluene oralkylnaphthalenes, chlorinated aromatics and chlorinated aliphatichydrocarbons, such as chlorobenzens, chloroethylenes or methylenechloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, forexample petroleum fractions, mineral and vegetable oils, alcohols, suchas butanol or glycol as well as their ethers and esters, ketones, suchas acetone, methyl ethyl ketone, methyl isobutyl ketone orcyclohexanone, strongly polar solvents, such as dimethylformamide anddimethylsulphoxide, as well as water.

As solid carriers there are suitable: for example ammonium salts andground natural minerals, such as kaolins, clays, talc, chalk, quartz,attapulgite, montmorillonite or diatomaceous earth, and ground syntheticminerals, such as highly disperse silicic acid, alumina and silicates,as solid carriers for granules there are suitable: for example crushedand fractionated natrual rocks such as calcite, marble, pumice,sepiolite and dolomite, as well as synthetic granules of inorganic andorganic, meals, and granules of organic material such as sawdust,coconut shells, corn cobs and tobacco stalks; as emulsifying and/orfoam-forming agents there are suitable: for example non-ionic andanionic emulsifiers, such as polyoxyethylene-fatty acid esters,polyoxyethylene-fatty alcohol ethers, for example alkylaryl polyglycolethers, alkylsulphonates, alkylsulphates, arylsulphonates as well asalbumin hydrolysation products; as dispersing agents there are suitable:for example lignin-sulphite waste liquors and methylcellulose.

Adhesives such as carboxymethylcellulose and natural and syntheticpolymers in the form of powders, granules or latices, such as gumarabic, polyvinyl alcohol and polyvinyl acetate, as well as naturalphospholipids, such as cephalins and lecithins, and syntheticphospholipids, can be used in the formulations. Further additives can bemineral and vegetable oils.

It is possible to use colorants such as inorganic pigments, for exampleiron oxide, titanium oxide and Prussian Blue, and organic dyestuffs,such as alizarin dyestuffs, azo dyestuffs and metal phthalocyaninedyestuffs, and trace nutrients such as salts of iron, manganese, boron,copper, cobalt, molybdenum and zinc.

The formulations in general contain between 0.1 and 95 per cent byweight of active compound, preferably between 0.5 and 90%.

The active compounds according to the invention, as such or in the formof their formulations, can also be used, for combating weeds, asmixtures with known herbicides, finished formulations or tank mixesbeing possible.

Possible components for the mixtures are known herbicides, such as, forexample,1-amino-6-ethylthio-3-(2,2-dimethylpropyl)-1,3,5-triazine-2,4(1H,3H)-dione(AMETHYDIONE) or N-(2-benzothiazolyl)-N,N'-dimethyl-urea(METABENZTHIAZURON) for combating weeds in cereals;4-amino-3-methyl-6-phenyl-1,2,4-triazin-5(4H)-one (METAMITRON) forcombating weeds in sugar beets and4-amino-6-(1,1-dimethylethyl)-3-methylthio-1,2,4-triazin-5(4H)-one(METRIBUZIN) for combating weeds in soy beans. Other possible mixturesare those with 2,4-dichlorophenoxyacetic acid (2,4-D);4-(2,4-dichlorophenoxy)-butyric acid (2,4-DB);2,4-dichlorophenoxypropionic acid (2,4-DP);N-(methoxymethyl)-2,6-diethyl-chloroacetanilide ALACHLOR);2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine (ATRAZINE); methyl5-(2,4-dichlorophenoxy)-2-nitrobenzoate (BIFENOX);3,5-dibromo-4-hydroxy-benzonitrile (BROMOXYNIL);2-chloro-N-{[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-amino]-carbonyl}-benzenesulphonamide(CHLORSULFURON); N,N-dimethyl-N'-(3-chloro-4-methylphenyl)-urea(CHLORTOLURON);2-chloro-4-ethylamino-6-(3-cyanopropylamino)-1,3,5-triazine (CYANAZINE);2-[4-(2,4-dichlorophenoxy)-phenoxy]-propionic acid, its methyl ester orits ethyl ester (DICLOFOP); 3,6-dichloro- 2-pyridinecarboxylic acid(CLOPYRALID); S-ethyl N,N-di-n-propyl-thiocarbamate (EPTAME);4-amino-6-t-butyl-3-ethylthio-1,2,4-triazin-5(4H)-one (ETHIOZIN);2-{4-[(6-chloro-2-benzoxazolyl)-oxy]-phenoxy}-propanoic acid, its methylester or its ethyl ester (FENOXAPROP);[(4-amino-3,5-dichloro-6-fluoro-2-pyridinyl)-oxy]-acetic acid or its1-methylheptyl ester (FLUROXYPYR); methyl2-[4,5-dihydro-4-methyl-4-(1-methylethyl)-5-oxo-1H-imidazol-2-yl]-4(5)-methylbenzoate(IMAZAMETHABENZ); 3,5-diiodo-4-hydroxybenzonitrile (IOXYNIL);N,N-dimethyl-N'-(4-isopropylphenyl)-urea (ISOPROTURON);(2-methyl-4-chlorophenoxy)-acetic acid (MCPA);(4-chloro-2-methylphenoxy)propionic acid (MCPP);N-methyl-2-(1,3-benzothiazol-2-yloxy)-acetanilide (MEFENACET);2-ethyl-6-methyl-N-(1-methyl-2-methoxyethyl)-chloroacetanilide(METOLACHLOR);2-{[((4-methoxy-6-methyl-1,3,5-triazin-2-yl)-amino)carbonyl]-amino]-sulphonyl}-benzoicacid or its methyl ester (METSULFURON); 2-chloro-4-trifluoromethylphenyl3-ethoxy-4-nitro-phenyl ether (OXYFLUORFEN);N-(1-ethylpropyl)-3,4-dimethyl-2,6-dinitroaniline (PENDIMETHALIN);2-chloro-N-isopropylacetanilide (PROPACHLOR);O-(6-chloro-3-phenyl-pyridazin-4-yl) S-octyl thiocarbonate (PYRIDATE);2-chloro-4,6-bis-(ethylamino)-1,3,5-triazine (SIMAZINE);4-ethylamino-2-t-butylamino-6-methylthio-s-triazine (TERBUTRYNE); methyl3-[[[[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-amino]-carbonyl]-amino]-sulphonyl]thiophene-2-carboxylate(THIAMETURON); S-(2,3,3-trichloroallyl) N,N-diisopropylthiolcarbamate(TRI-ALLATE) and 2,6-dinitro-4-trifluoromethyl-N,N-dipropylaniline(TRIFLURALIN). Surprisingly, some mixtures also show a synergisticaction.

Mixtures with other known active compounds, such as fungicides,insecticides, acaricides, nematicides, bird repellents, plant nutrientsand agents which improve soil structure, are also possible.

The active compounds can be used as such, in the form of theirformulations or in the use forms prepared therefrom by further dilution,such as ready-to-use solutions, suspensions, emulsions, powders, pastesand granules. They are used in the customary manner, for example bywatering, spraying, atomizing or scattering.

The active compounds according to the invention can be applied eitherbefore or after emergence of the plants.

They can also be incorporated into the soil before sowing.

The amount of active compound used can vary within a substantial range.It depends essentially on the nature of the desired effect. In general,the amounts used are between 0.01 and 10 kg of active compound perhectare of soil surface, preferably between 0.05 and 5 kg per ha.

The preparation and use of the active compounds according to theinvention can be seen from the following examples.

PREPARATION EXAMPLES EXAMPLE 1 ##STR254##

20 ml of concentrated hydrochloric acid are added to 11.1 g (0.04 mol)of1-(N-isobutylcarbamoyl)-4-isopropylideneimino-3-methyl-1,2,4-triazolin-5-onein 100 ml of ethanol and the solution is concentrated at 60° C. andabout 200 mbar in the course of 5 hours on a rotary evaporator. Theresidue is brought to crystallization by trituration withethanol/diethyl ether (1:1) and dried in air. 4.3 g (50% of theory) of4-amino-1-(N-isobutylcarbamoyl)-3-methyl-triazolin-5-one of meltingpoint 183° C. are obtained.

EXAMPLE 2 ##STR255##

3.6 g (0.036 mol) of t-butyl isocyanate and 0.05 g to 0.1 g ofdiazabicycloundecene (DBU) are added to 3.42 g (0.03 mol) of4-amino-3-methyl-1,2,4-(1H)-triazolin-5-one in 80 ml of absoluteacetonitrile, the mixture is stirred for 2 hours at 20° C., concentratedin vacuo and the residue taken up in dichloromethane, the solution iswashed with water, dried over sodium sulphate and concentrated in vacuoand the residue is crystallized by trituration with diethyl ether.

5.0 g (78.3% of theory) of4-amino-1-(N-t-butylcarbamoyl)-3-methyl-1,2,4-triazolin-5-one of amelting point of 132° C. are obtained.

EXAMPLE 3 ##STR256##

4.2 g (0.03 mol) of (2,2-dichlorocyclopropyl)methylamine are added to8.2 g (0.03 mol) of4-isopropylideneimino-3-methyl-1-phenoxycarbonyl-1,2,4-triazolin-5-onein 50 ml of absolute tetrahydrofuran, the mixture is then stirred for 12hours at 20° C., concentrated in vacuo and the residue taken up in 100ml of ethanol, 3 ml of concentrated hydrochlorid acid are added to thesolution which is stirred for 3 to 4 hours at 60° C. and 200 mbar. Forthe working up the mixture is concentrated in vacuo, the residue istaken up in dichloromethane and the solution is washed three times witha saturated aqueous sodium hydrogen carbonate solution, dried oversodium sulphate and concentrated in vacuo. The residue is crystallizedin vacuo. The residue is crystallized out by trituration with diethylether.

4.4 g (52% of theory) of4-amino-1-[N-(2,2-dichlorocyclopropylmethyl)-carbamoyl]-3-methyl-1,2,4-triazolin-5-oneof a melting point of 149° C. are obtained.

EXAMPLE 4 ##STR257##

8.9 g (0.088 mol) of 1,1-dimethylbutylamine are added to 3.2 g (0.0137mol) of 4-amino-3-methyl-1-phenoxycarbonyl-1,2,4-triazolin-5-one in amixture of 25 ml of tetrahydrofuran and 10 ml of dioxane, the mixture isheated to reflux temperature for 24 hours, concentrated in vacuo and theresidue taken up in dichloromethane, the solution is washed with 2%sodium hydroxide solution and water, dried over sodium sulphate, thesolvent removed in vacuo and the residue crystallized by triturationwith diethyl ether.

1.9 g (61% of theory) of4-amino-1-[N-(1,1-dimethylbutyl)-carbamoyl]-3-methyl-1,2,4-triazolin-5-oneof a melting point of 110° C. are obtained.

The following substituted triazolinones of the general formula (I)##STR258## are obtained in a corresponding manner and according to thegeneral instructions for the preparation:

                                      TABLE 1                                     __________________________________________________________________________    Example No.                                                                          R.sup.1                                                                           R.sup.2         X Y physical properties                            __________________________________________________________________________     5     CH.sub.3                                                                           ##STR259##     O O .sup.1 H-NMR*.sup.) 1.5 (d)                     6     CH.sub.3                                                                           ##STR260##     O O .sup.1 H-NMR*.sup.) 1.5 (d)                     7     C.sub.2 H.sub.5                                                                    ##STR261##     O O mp. 139° C.                              8     H                                                                                  ##STR262##     O O mp. 161° C.                              9     CH.sub.3                                                                          CH(CH.sub.3).sub.2                                                                            O O mp. 63° C.                              10     CH.sub.3                                                                          (CH.sub.2).sub.5CH.sub.2 Cl                                                                   O O .sup.1 H-NMR*.sup.).sup.)                                                     1.45 (m, 4H)                                   11     CH.sub.3                                                                           ##STR263##     O O .sup.1 H-NMR*.sup.) 0.95 (t, CH.sub.3 )        12     CH.sub.3                                                                           ##STR264##     O O mp. 133° C.                             13     CH.sub.3                                                                          CH(C.sub.2 H.sub.5).sub.2                                                                     O O mp. 103° C.                             14     CH.sub.3                                                                           ##STR265##     O O mp. 103° C.                             15     CH.sub.3                                                                           ##STR266##     O O mp. 105° C.                             16     CH.sub.3                                                                           ##STR267##     O O mp. 135° C.                             17     CH.sub.3                                                                           ##STR268##     O O mp. 106° C. (decomp.)                   18     CH.sub.3                                                                           ##STR269##     O O n.sub.D.sup.20 1.5496                          19     CH.sub.3                                                                           ##STR270##     S O mp. 128° C.                             20     CH.sub.3                                                                           ##STR271##     S O mp. 100° C.                             21     H   (CH.sub.2).sub.5CH.sub.2 Cl                                                                   O O mp. 131° C.                             22     CH.sub.3                                                                           ##STR272##     O O mp. 153° C.                             23     CH.sub.3                                                                           ##STR273##     O O mp. 118° C.                             24     CH.sub.3                                                                          CH.sub.2CHCH.sub.2                                                                            O O mp. 92° C.                              25     CH.sub.3                                                                           ##STR274##     O O mp. 127° C.                             26     CH.sub.3                                                                           ##STR275##     O O n.sub.D.sup.22 1.5055                          27     CH.sub.3                                                                           ##STR276##     O O mp. 176° C.                             28     C.sub.2 H.sub.5                                                                    ##STR277##     O O .sup.1 H-NMR*.sup.): 4.4; 7.95                 29     CH.sub.3                                                                           ##STR278##     O O mp. 133° C.                             30     C.sub.2 H.sub.5                                                                    ##STR279##     O O mp. 30-40° C.                           31     CH.sub.3                                                                           ##STR280##     O O .sup.1 H-NMR*.sup.); 4.36; 8.23                32     CH.sub.3                                                                           ##STR281##     O O mp. 99° C.                              33     CH.sub.3                                                                           ##STR282##     O O .sup.1 H-NMR*.sup.): 4.40; 7.61                34     CH.sub.3                                                                           ##STR283##     O O mp. 162° C.                             35     CH.sub.3                                                                           ##STR284##     O O mp. 198° C.                             36     CH.sub.3                                                                          (CH.sub.2).sub.3CH.sub.3                                                                      O O mp. 108-109° C.                         37     CH.sub.3                                                                          CH.sub.3        O O mp. 168-170° C.                         38     CH.sub.3                                                                          (CH.sub.2).sub.2CH.sub.3                                                                      O O mp. 134-136° C.                         39     CH.sub.3                                                                           ##STR285##     O O mp. 149° C.                             40     CH.sub.3                                                                           ##STR286##     O O mp. 149-151° C.                         41     CH.sub.3                                                                           ##STR287##     O O mp. 93-94° C.                           42     CH.sub.3                                                                          CH.sub.2CH.sub.2CN                                                                            O O mp. 175-178° C.                         43     CH.sub.3                                                                           ##STR288##     O O mp. 91-92° C.                           44     C.sub.2 H.sub.5                                                                    ##STR289##     O O mp. 102-103° C.                         45     CH.sub.3                                                                           ##STR290##     O O mp. 178° C.                             46     CH.sub.3                                                                           ##STR291##     O O mp. 113° C.                             47     CH.sub.3                                                                           ##STR292##     O O mp. 109° C.                             48     CH.sub.3                                                                           ##STR293##     O O mp. 148° C.                             49     CH.sub.3                                                                           ##STR294##     O O .sup.1 H-NMR*.sup.): 0.35-0.6; 0.93            50     CH.sub.3                                                                           ##STR295##     O O mp. 175° C.                             51     CH.sub.3                                                                           ##STR296##     O O mp. 211° C. (hydrochloride)             52     CH.sub.3                                                                           ##STR297##     O O mp. 152° C.                             53     CH.sub.3                                                                          C.sub.2 H.sub.5 O O mp. 185° C.                             54     CH.sub.3                                                                           ##STR298##     O O mp. 198° C. (hydrochloride)             55     CH.sub.3                                                                           ##STR299##     O O mp. 135° C.                             56     CH.sub.3                                                                           ##STR300##     O O mp. 200-203° C.                         57     CH.sub.3                                                                           ##STR301##     O O mp. 119° C.                             58     CH.sub.3                                                                           ##STR302##     O O mp. 136° C.                             59     CH.sub.3                                                                           ##STR303##     O O mp. 122° C.                             60     CH.sub.3                                                                           ##STR304##     O O mp. 141° C.                             61     CH.sub.3                                                                           ##STR305##     O O mp. 176° C.                             62     CH.sub.3                                                                           ##STR306##     O O mp. 67° C.                              63     CH.sub.3                                                                           ##STR307##     O O mp. 120° C.                             64     CH.sub.3                                                                          (CH.sub.2).sub.2OCH.sub.3                                                                     O O mp. 114° C.                             65     CH.sub.3                                                                           ##STR308##     O O mp. 84° C. (hydrochloride)              66     CH.sub.3                                                                          (CH.sub.2).sub.3CH.sub.3                                                                      O S mp. 147° C.                             67     CH.sub.3                                                                           ##STR309##     O S mp. 195° C.                             68     CH.sub.3                                                                          C.sub.2 H.sub.5 O S mp. 205° C.                             69     CH.sub.3                                                                          CH.sub.3        O S mp. 212° C.                             70     CH.sub.3                                                                           ##STR310##     O O mp. 139° C.                             71     CH.sub.3                                                                           ##STR311##     O O mp. 114° C.                             72     CH.sub.3                                                                           ##STR312##     O O n.sub.D.sup.20 1.5328                          73     CH.sub.3                                                                           ##STR313##     O O mp. 120° C.                             74     CH.sub.3                                                                           ##STR314##     O O n.sub.D.sup.20 1.3840                          75     CH.sub.3                                                                           ##STR315##     O O mp. 158° C.                                         ##STR316##                                                        76     CH.sub.3                                                                           ##STR317##     O O mp. 147° C.                             77     CH.sub.3                                                                           ##STR318##     O O n.sub.D.sup.22 1.4995 (hydrochloride)          78     CH.sub.3                                                                           ##STR319##     O O n.sub.D.sup.22 1.4891                          79     CH.sub.3                                                                           ##STR320##     O O n.sub.D.sup.20 1.4920                          80     CH.sub.3                                                                           ##STR321##     O O mp. 140° C.                             81     CH.sub.3                                                                           ##STR322##     O O mp. 115° C.                             82     CH.sub.3                                                                           ##STR323##     O O mp. 134° C.                             83     CH.sub.3                                                                           ##STR324##     O O mp. 164° C.                             84     CH.sub.3                                                                           ##STR325##     O O mp. 144° C.                             85     CH.sub. 3                                                                          ##STR326##     O O mp. 121° C.                             86     CH.sub.3                                                                           ##STR327##     O O .sup.1 H-NMR*.sup.): 2.33                      87     CH.sub.3                                                                          CH.sub.2CF.sub.3                                                                              O O mp. 152° C.                             88     CH.sub.3                                                                           ##STR328##     O S mp. 178° C.                             89     CH.sub.3                                                                           ##STR329##     O O mp. 156° C.                             90     CH.sub.3                                                                           ##STR330##     O O mp. 167° C.                             91     CH.sub.3                                                                           ##STR331##     O O mp. 113° C.                             92     CH.sub.3                                                                           ##STR332##     O O mp. 133° C.                             93     CH.sub.3                                                                           ##STR333##     O O mp. 98° C.                              94     CH.sub.3                                                                           ##STR334##     O O mp. 156° C.                             95     CH.sub.3                                                                           ##STR335##     O O mp. 210° C.                             96     CH.sub.3                                                                           ##STR336##     O O mp. 175° C.                             97     CH.sub.3                                                                           ##STR337##     O O mp. 106° C.                             98     CH.sub.3                                                                          (CH.sub.2).sub.2CH(CH.sub.3).sub.2                                                            O O mp. 104° C.                             99     CH.sub.3                                                                           ##STR338##     O O mp. 120° C. (decomp.)                   100    CH.sub.3                                                                           ##STR339##     O O mp. 108° C.                             101    CH.sub.3                                                                           ##STR340##     O O mp. 151° C.                             102    CH.sub.3                                                                           ##STR341##     O O mp. 151° C.                             103    CH.sub.3                                                                           ##STR342##     O O mp. 134° C.                             104    CH.sub.3                                                                           ##STR343##     O O n.sub.D.sup.20 1.4972                          105    CH.sub.3                                                                           ##STR344##     O O mp. 128° C.                             106    CH.sub.3                                                                           ##STR345##     O O mp. 101° C.                             107    CH.sub.3                                                                           ##STR346##     O O mp. 73° C.                              108    CH.sub.3                                                                           ##STR347##     O O n.sub.D.sup.20 1.5815 (hydrochloride)          109    CH.sub.3                                                                           ##STR348##     O O mp. 210° C. (hydrochloride)             110    CH.sub.3                                                                           ##STR349##     O O mp. 145° C.                             111    CH.sub.3                                                                           ##STR350##     O O n.sub.D.sup.20 1.4890                          112    CH.sub.3                                                                           ##STR351##     O O n.sub.D.sup.20 1.4858                          113    CH.sub.3                                                                           ##STR352##     O O mp. 108° C. (hydrochloride)             114    CH.sub.3                                                                          (CH.sub.2).sub.4CH.sub.3                                                                      O O mp. 81° C.                              115    CH.sub.3                                                                           ##STR353##     O O n.sub.D.sup.20 1.5100 (hydrochloride)          116    CH.sub.3                                                                           ##STR354##     O O n.sub.D.sup.20 1.5150 (hydrochloride)          117    CH.sub.3                                                                           ##STR355##     O O mp. 157° C.                             118    CH.sub.3                                                                           ##STR356##     O O mp. 116° C.                             119    CH.sub.3                                                                           ##STR357##     O O mp. 145° C.                             120    CH.sub.3                                                                           ##STR358##     O O mp. 118° C.                             121    CH.sub.3                                                                          CH.sub.2CH.sub.2OC.sub.2 H.sub.5                                                              O O mp. 123° C.                             122    CH.sub.3                                                                           ##STR359##     O O mp. 213° C.                             123    CH.sub.3                                                                           ##STR360##     O O mp. 93° C.                              124    CH.sub.3                                                                           ##STR361##     O O mp. 93° C.                              125    CH.sub.3                                                                           ##STR362##     O O .sup.1 H-NMR*.sup.): 1.58 (dd); 1.77 (t);                                     2.76 (t)                                       126    CH.sub.3                                                                           ##STR363##     O O mp. 142° C.                             127    CH.sub.3                                                                           ##STR364##     O O mp. 123° C. (endo-Form)                 128    CH.sub.3                                                                           ##STR365##     O O mp. 131° C.                             129    CH.sub.3                                                                           ##STR366##     O O mp. 133° C.                             130    CH.sub.3                                                                           ##STR367##     O O mp. 125° C.                             131    CH.sub.3                                                                           ##STR368##     O O mp. 117° C.                             132    CH.sub.3                                                                           ##STR369##     O O .sup.1 H-NMR*.sup.): 1.45 (s); 7.04-7.43                                      (m)                                            133    CH.sub.3                                                                           ##STR370##     O O mp. 168° C.                             134    CH.sub.3                                                                           ##STR371##     O O mp. 118° C.                             135    CH.sub.3                                                                           ##STR372##     O O mp. 157° C.                             136    CH.sub.3                                                                           ##STR373##     O O mp. 180° C.                             137    CH.sub.3                                                                           ##STR374##     O O mp. 188° C.                             138    CH.sub.3                                                                           ##STR375##     O O mp. 95° C.                              139    C.sub.2 H.sub.5                                                                   C(CH.sub.3).sub.3                                                                             O O m.p. 158° C.                            140    C.sub.2 H.sub.5                                                                    ##STR376##     O O m.p. 119° C.                            141    C.sub.2 H.sub.5                                                                    ##STR377##     O O m.p. 106° C.                            142    C.sub.2 H.sub.5                                                                   CH(CH.sub.3).sub.2                                                                            O O m.p. 89° C.                             143    C.sub.2 H.sub.5                                                                    ##STR378##     O O n.sub.D.sup.22 1.4929                          144    C.sub.2 H.sub.5                                                                    ##STR379##     O O n.sub.D.sup.22 1.4955                          145    CH.sub.3                                                                           ##STR380##     O O m.p. 146° C.                            146    C.sub.2 H.sub.5                                                                    ##STR381##     O O m.p. 105° C.                            147    CH.sub.3                                                                          (CH.sub.2).sub.11CH.sub.3                                                                     O O m.p. 110° C.                            148    CH.sub.3                                                                          (CH.sub.2).sub.15CH.sub.3                                                                     O O m.p. 98° C.                             149    CH.sub.3                                                                          (CH.sub.2).sub.17CH.sub.3                                                                     O O m.p. 104° C.                            150    CH.sub.3                                                                           ##STR382##     O O m.p. 118° C.                            151    CH.sub.3                                                                           ##STR383##     O O m.p. 129° C.                            152    CH.sub.3                                                                           ##STR384##     O O m.p. 112°  C.                           153    CH.sub.3                                                                           ##STR385##     O O m.p. 193° C.                            154    CH.sub.3                                                                           ##STR386##     O O m.p. 125° C.                            155    C.sub.2 H.sub.5                                                                    ##STR387##     O O n.sub.D.sup.20 1.4896                          156    CH.sub.3                                                                           ##STR388##     O O m.p. 185° C.                            157    CH.sub.3                                                                           ##STR389##     O O m.p. 158° C.                            158    CH.sub.3                                                                           ##STR390##     O O m.p. 132° C.                            159    CH.sub.3                                                                           ##STR391##     O O m.p. 98° C.                             160    CH.sub.3                                                                           ##STR392##     O O m.p. 137° C.                            161    CH.sub.3                                                                           ##STR393##     O O m.p. 162° C.                            162    CH.sub.3                                                                           ##STR394##     O O m.p. 172° C.                            163    C.sub.2 H.sub.5                                                                    ##STR395##     O O m.p. 104° C.                            __________________________________________________________________________     *.sup.) The .sup.1 HNMR spectra were recorded in deuterochloroform            (CDCl.sub.3) using tetramethylsilane (TMS) as the internal standard. The      chemical shift is given as the δ-value in ppm.                     

EXAMPLE 164 ##STR396##

6.1 g (0.055 mol) of cyclopentyl isocyanate and a small amount ofdiazabicycloundecene (DBU) are added to 7.1 g (0.05 mol) of4-amino-3-isopropyl-(1H)-1,2,4-triazolin-5-one in 100 ml of absoluteacetonitrile, the mixture is stirred for 12 hours at room temperatureand then concentrated in vacuo, the residue is taken up indichloromethane, the solution is washed with water to neutrality, driedover magnesium sulphate and concentrated, and the residue iscrystallized by trituration with diethyl ether.

10.0 g (78% of theory) of4-amino-1-(N-cyclopentylcarbamoyl)-3-isopropyl-1,2,4-triazolin-5-one ofmelting point 109° C. are obtained.

EXAMPLE 165 ##STR397##

5.5 g (0.05 mol) of 3-methyl-3-butinyl isocyanate and a small amount ofdiazabicycloundecene (DBU) are added to 11.1 g (0.05 mol) of4-(4-methylpent-2-ylideneimino)-3-cyclopropyl-1,2,4-(1H)-triazolin-5-onein 150 ml of absolute acetonitrile, the mixture is stirred for 12 hoursat 20° C. and subsequently concentrated in vacuo, the residue is takenup in aqueous ethanol, 2 ml of concentrated hydrochloric acid are added,the mixture is slowly concentrated at 60° C. under reduced pressure, theresidue is taken up in dichloromethane, the solution is washed usingsaturated sodium hydrogen carbonate solution, dried over magnesiumsulphate and concentrated, and the residue is crystallized bytrituration with diethyl ether.

10.4 g (84% of theory) of4-amino-3-cyclopropyl-1-[N-(3-methyl-3-butinyl)-carbamoyl]-1,2,4-triazolin-5-oneof melting point 160° C. are obtained.

The following substituted triazolinones of the general formula (I) areobtained in a corresponding manner and following the general preparationinstructions:

    __________________________________________________________________________     ##STR398##                          (I)                                      Ex.                                                                           No.                                                                              R.sup.1  R.sup.2       Physical constant                                   __________________________________________________________________________    166                                                                              (CH.sub.3).sub.3 C                                                                     (CH.sub.2).sub.5CH.sub.3                                                                    n.sub.D.sup.20 : 1.4980                             167                                                                              CH.sub.3(CH.sub.2).sub.2                                                                ##STR399##   m.p 106° C.                                  168                                                                              (CH.sub.3).sub.2 CH                                                                     ##STR400##   m.p. 90° C.                                  169                                                                              (CH.sub.3).sub.2 CH                                                                     ##STR401##   m.p. 133° C.                                 170                                                                              CH.sub.3(CH.sub.2).sub.2                                                                ##STR402##   m.p. 98° C.                                  171                                                                              (CH.sub.3).sub.3 C                                                                      ##STR403##   m.p. 158° C.                                 172                                                                              CH.sub.3(CH.sub.2).sub.2                                                                ##STR404##   m.p. 100° C.                                 173                                                                              (CH.sub.3).sub.2 CH                                                                     ##STR405##   n.sub.D.sup.20 : 1.5168                             174                                                                              CH.sub.3(CH.sub.2).sub.2                                                                ##STR406##   n.sub.D.sup.20 : 1.5890                             175                                                                              (CH.sub.3).sub.2 CH                                                                     ##STR407##   n.sub.D.sup.20 : 1.5650                             176                                                                              (CH.sub.3).sub.3 C                                                                      ##STR408##   .sup.1 H-NMR*.sup.) : 1,44(9H), 4,48(2H)            177                                                                              (CH.sub.3).sub.3 C                                                                      ##STR409##   .sup.1 H-NMR*.sup.) : 1,44(9H), 4,53(2H)            178                                                                              (CH.sub.3).sub.3 C                                                                     C(CH.sub.3).sub.3                                                                           m.p. 142° C.                                 179                                                                              (CH.sub.3).sub.3 C                                                                      ##STR410##   m.p. 203° C.                                 180                                                                              CH.sub.3(CH.sub.2).sub.2                                                               C(CH.sub.3).sub.3                                                                           m.p. 112° C.                                 181                                                                              (CH.sub.3).sub.2 CH                                                                    C(CH.sub.3).sub.3                                                                           m.p. 108° C.                                 182                                                                               ##STR411##                                                                            C(CH.sub.3).sub.3                                                                           m.p. 151° C.                                 183                                                                              (CH.sub.3).sub.3 C                                                                      ##STR412##   n.sub.D.sup.20 : 1.5171                             184                                                                              (CH.sub.3).sub.3 C                                                                      ##STR413##   n.sub.D.sup.20 : 1.5411                             185                                                                              (CH.sub.3).sub.3 C                                                                      ##STR414##   m.p. 133° C.                                 186                                                                              (CH.sub.3).sub.3 C                                                                      ##STR415##   m.p. 148° C.                                 187                                                                              (CH.sub.3).sub.3 C                                                                      ##STR416##   n.sub.D.sup.20 : 1.4844                             188                                                                              (CH.sub.3).sub.3 C                                                                      ##STR417##   m.p. 135° C.                                 189                                                                              (CH.sub.3).sub.3 C                                                                      ##STR418##   m.p. 141° C.                                 190                                                                              (CH.sub.3).sub.3 C                                                                      ##STR419##   m.p. 208° C.                                 191                                                                              (CH.sub.3).sub.3 C                                                                      ##STR420##   n.sub.D.sup.20 : 1.5520                             192                                                                              (CH.sub.3).sub.3 C                                                                      ##STR421##   m.p. 172° C.                                 193                                                                              (CH.sub.3).sub.2 CH                                                                     ##STR422##   m.p. 83° C.                                  194                                                                              (CH.sub.3).sub.2 CH                                                                     ##STR423##   n.sub.D.sup.20 : 1.4801                             195                                                                               ##STR424##                                                                             ##STR425##   m.p. 177° C.                                 196                                                                               ##STR426##                                                                             ##STR427##   m.p. 107° C.                                 197                                                                              (CH.sub.3).sub.2 CH                                                                     ##STR428##   m.p. 124° C.                                 198                                                                              (CH.sub.3).sub.2 CH                                                                     ##STR429##   .sup.1 H-NMR*.sup.) : 1,34(6H), 3,12(1H),                                     4,40(2H)                                            199                                                                              (CH.sub.3).sub.2 CH                                                                     ##STR430##   m.p. 121° C.                                 200                                                                              (CH.sub.3).sub.2 CH                                                                    CH(CH.sub.3).sub.2                                                                          m.p. 124° C.                                 201                                                                              (CH.sub.3).sub.2 CH                                                                     ##STR431##   n.sub.D.sup.20 : 1.4874                             202                                                                              (CH.sub.3).sub.2 CH                                                                     ##STR432##   n.sub.D.sup.20 : 1.4847                             203                                                                              (CH.sub.3).sub.2 CH                                                                     ##STR433##   n.sub.D.sup.20 : 1.4860                             204                                                                              (CH.sub.3).sub.2 CH                                                                     ##STR434##   n.sub.D.sup.20 : 1.5308                             205                                                                              (CH.sub.3).sub.2 CH                                                                     ##STR435##   n.sub.D.sup.20 : 1.5355                             206                                                                              (CH.sub.3).sub.2 CH                                                                     ##STR436##   n.sub.D.sup.20 : 1.5011                             207                                                                               ##STR437##                                                                             ##STR438##   m.p. 94° C.                                  208                                                                               ##STR439##                                                                             ##STR440##   m.p. 138° C.                                 209                                                                              (CH.sub.3).sub.2 CH                                                                     ##STR441##   amorphous δ = 1.34 Duplett (2CH.sub.3)                                  3.13 Multiplett (1H)  3.90 Multiplett (2H) 4.48                               Singulett (NH.sub.2) 8.04 Duplett (NH)              210                                                                               ##STR442##                                                                             ##STR443##   amorphous δ = 1.05 Multiplett (2H,                                      cyclopropyl 1.16 Multiplett (2H, cyclopropyl)                                 2.06 Multiplett (1H, cyclopropyl) 3.89                                        Multiplett (2H) 4.55 Singulett (NH.sub.2) 8.03                                Duplett (NH)                                        211                                                                              (CH.sub.3).sub.2 CH                                                                    C.sub.4 H.sub.9 -n                                                                          n.sub.D.sup.20 : 1.4969                             212                                                                               ##STR444##                                                                            C.sub.4 H.sub.9 -n                                                                          mp: 84° C.                                   __________________________________________________________________________     *.sup.) The .sup.1 HNMR spectra were recorded in deuterochloroform            (CDCl.sub.3) with tetramethylsilane (TMS) as the internal standard. The       chemical shift is indicated as a δ value in ppm.                   

PREPARATION OF THE STARTING COMPOUNDS EXAMPLE II-1 ##STR445##

12 g (0.12 mol) of isobutyl isocyanate are added dropwise at 20° C. withstirring to 6 g (0.04 mol) of4-isopropylideneimino-3-methyl-1H-triazolin-5-one and 4 g (0.04 mol) oftriethylamine in 20 ml of dioxane and the mixture is stirred for 3 hoursat 100° C. after completion of the addition. For working up, thereaction mixture is concentrated in vacuo, the residue is taken up in100 ml of dichloromethane, and the solution is washed repeatedly with100 ml of water in each case, dried over sodium sulphate and freed fromsolvent in vacuo.

11.2 g (100% of theory) of1-(N-isobutylcarbamoyl)-4-isopropylideneimino-3-methyl-1,2,4-triazolin-5-oneare obtained as an oil.

¹ H-NMR (CDCl₃): δ=0.85 (d, 6H) ppm.

The following initial products of the general formula (II) ##STR446##are obtained in a corresponding manner and according to the generalinstructions for the preparation:

                                      TABLE 2                                     __________________________________________________________________________     No:Example                                                                         R.sup.1                                                                          R.sup.2                                                                                  ##STR447##   X                                                                               Y                                                                               propertiesphysical                       __________________________________________________________________________    II-2 CH.sub.3                                                                          ##STR448##                                                                              C(CH.sub.3).sub.2                                                                          O O mp. 125° C.                        II-3 CH.sub.3                                                                          ##STR449##                                                                              CHCH(CH.sub.3).sub.2                                                                       O O .sup.1 H-NMR*) 3.9                        II-4 CH.sub.3                                                                          ##STR450##                                                                              C(CH.sub.3).sub.2                                                                          O O mp. 87° C                          II-5 CH.sub.3                                                                         CH(CH.sub.3).sub.2                                                                       C(CH.sub.3).sub.2                                                                          O O mp. 107° C.                        II-6 CH.sub.3                                                                         CH(C.sub.2 H.sub.5).sub.2                                                                C(CH.sub.3).sub.2                                                                          O O mp. 68° C.                         II-7 CH.sub.3                                                                         CHCH(CH.sub.3).sub.2                                                                     C(CH.sub.3).sub.2                                                                          O O .sup.1 H-NMR*) 0.54 (d, CH.sub.3)         II-8 CH.sub.3                                                                          ##STR451##                                                                              C(CH.sub.3).sub.2                                                                          O O mp. 115° C.                        II-9 CH.sub.3                                                                          ##STR452##                                                                              C(CH.sub.3).sub.2                                                                          O O mp. 88° C.                         II-10                                                                              CH.sub.3                                                                          ##STR453##                                                                              C(CH.sub.3).sub.2                                                                          O O mp. 139° C.                        II-11                                                                              CH.sub.3                                                                          ##STR454##                                                                              C(CH.sub.3).sub.2                                                                          O O oil                                       II-12                                                                              CH.sub.3                                                                         CH.sub.2COOC.sub.2 H.sub.5                                                               C(CH.sub.3).sub.2                                                                          O O mp. 108° C.                        II-13                                                                              CH.sub.3                                                                         CH.sub.2CHCH.sub.2                                                                       C(CH.sub.3).sub.2                                                                          O O mp.86° C.                          II-14                                                                              CH.sub.3                                                                          ##STR455##                                                                              C(CH.sub.3).sub.2                                                                          O O mp. 158° C.                        II-15                                                                              CH.sub.3                                                                          ##STR456##                                                                              C(CH.sub.3).sub.2                                                                          O O mp. 218° C.                        II-16                                                                              CH.sub.3                                                                          ##STR457##                                                                              C(CH.sub.3).sub.2                                                                          O O mp. 185° C.                        II-17                                                                              CH.sub.3                                                                          ##STR458##                                                                              C(CH.sub.3).sub.2                                                                          O O mp. 121-122° C.                    __________________________________________________________________________     No:Example                                                                         R.sup.1                                                                          R.sup.2                                                                                  ##STR459##   X                                                                               Y                                                                               point (°C.)melting                __________________________________________________________________________    II-18                                                                              CH.sub.3                                                                          ##STR460##                                                                               ##STR461##  O O 80                                        II-19                                                                              CH.sub.3                                                                          ##STR462##                                                                               ##STR463##  O O 137                                       II-20                                                                              CH.sub.3                                                                          ##STR464##                                                                               ##STR465##  O O 163                                       II-21                                                                              CH.sub.3                                                                          ##STR466##                                                                               ##STR467##  O O 77                                        __________________________________________________________________________

EXAMPLE III-1 ##STR468##

1892 g (8.84 mol) of diphenyl carbonate are added in portions to 884 g(17.68 mol) of hydrazine hydrate with stirring and ice-cooling, so thatthe temperature of the reaction mixture does not exceed 30° C. When theaddition is complete, the mixture is stirred for about 3 hours at 80°C., any reaction water formed during this process is removed in vacuo,760 g (8.84 mol) of cyclopropanecarboxylic acid are then added, themixture is subsequently heated to 200° C. in the course of 6 hours andunder an atmosphere of inert gas, and any reaction water liberated issimultaneously distilled off. When the reaction is complete, the mixtureis evaporated in vacuo to dryness, the residue is extracted using 3000ml of boiling ethanol, the extract is filtered and cooled, and thecrystalline precipitate which has formed is filtered off with suctionand dried.

420 g (34% of theory) of4-amino-3-cyclopropyl-1,2,4-(1H)-triazolin-5-one of melting point 181°C. are obtained.

The following are obtained in a corresponding manner:

EXAMPLE III-2 ##STR469##

melting point 168° C.

EXAMPLE III-3 ##STR470##

melting point 168° C.

EXAMPLE III-4 ##STR471## EXAMPLE III-5 ##STR472## EXAMPLE (III-6)##STR473##

melting point 261° C.

EXAMPLE III-7 ##STR474##

11.4 g (0.1 mol) of 4-amino-3-methyl-1H-1,2,4-triazolin-5-one (compareEurop. J. Med. Chem.: Chim. Ther. 18, 215-220 [1983]) and 0.1 g ofp-toluenesulphonic acid in 100 ml (79.06 g; 1.36 mol) of acetone arestirred at 70° C. for 40 hours, and the mixture is then concentrated invacuo, 15.4 g (100% of theory) of4-isopropylidene-imino-3-methyl-1H-1,2,4-triazolin-5-one of meltingpoint 140°-144° C. are obtained.

EXAMPLE VIII-1 ##STR475##

142 g (1.0 mol) of 4-amino-3-cyclopropyl-1,2,4-(1H)-triazolin-5-one in1000 ml of methyl isobutyl ketone with the addition of 100 mg ofp-toluenesulphonic acid are refluxed in a water separator until theliberation of further reaction water has ceased. For working up, themixture is concentrated in vacuo, and the residue is crystallized bytrituration with petroleum ether.

66 g (30% of theory) of4-(4-methylpent-2-ylideneimino)-3-cyclopropyl-1,2,4-(1H)-triazolin-5-oneof melting point 64° C. are obtained.

EXAMPLE X-1 ##STR476##

13.4 g (0.12 mol) of potassium-t-butylate are first added at roomtemperature to 15.4 g (0.1 mol) of4-isopropylideneimino-3-methyl-1,2,4-(1H)-triazolin-5-one in 100 ml ofabsolute tetrahydrofuran, the mixture is stirred for one hour at roomtemperature, 15.5 g (0.1 mol) of phenyl chloroformate are then added andthe mixture is stirred for a further 12 hours at 20° C.

For the working up the mixture is acidified with glacial acetic acid andconcentrated in vacuo, the residue is taken up in chloroform and thesolution is washed with water, dried over sodium sulphate, concentratedonce again in vacuo and the residue recrystallized from acetone.

10 g (36.5% of theory) of4-isopropylideneimino-3-methyl-1-phenoxycarbonyl-1,2,4-triazolin-5-oneof a melting point of 162° C. are obtained.

EXAMPLE X-2 ##STR477##

1.5 g (0.05 mol) of sodium hydride are added at 20° C. to 7.7 g (0.05mol) of 4-isopropylideneimino-3-methyl-1,2,4-(1H)-triazolin-5-one in 50ml of absolute tetrahydrofuran, the mixture is stirred for one hour atroom temperature and then 5.4 g (0.05 mol) of ethyl chloroformate areadded dropwise with stirring and when the addition has ended the mixtureis stirred at 20° C. for a further 12 hours.

For the working up the mixture is acidified with glacial acetic acid andconcentrated in vacuo, the residue is taken up in dichloromethane andthe solution is washed with water, dried over sodium sulphate,concentrated once again in vacuo and the residue recrystallized fromisopropanol.

5.0 g (44% of theory) of1-ethoxycarbonyl-4-isopropylideneimino-3-methyl-1,2,4-triazolin-5-one ofa melting point of 91° C. are obtained.

USE EXAMPLES

The compounds shown below were employed as the comparison substances inthe following use examples: ##STR478##4-Amino-3-methyl-6-phenyl-1,2,4-triazin-5-one (known from DE-OS (GermanPublished Specification) 2,364,474, Example I-22) ##STR479##N-Isobutyl-2-oxoimidazolidine-1-carboxamide (known from R. Wegler"Chemie der Pflanzenschutz-und Schadlingsbekampfungsmittel" Vol. 5, page219 (1977)). ##STR480##4-amino-1-(N-isopropylcarbamoyl)-3-methylthio(1H,4H)-1,2,4-triazolin-5-one##STR481##4-amino-1-(N-propylcarbamoyl)-3-methylthio-(1H,4H)-1,2,4-triazolin-5-one##STR482##4-amino-1-(N-butylcarbamoyl)-3-methylthio-(1H,4H)-1,2,4-triazolin-5-oneand ##STR483##4-amino-1-(N-cyclohexylcarbamoyl)-3-methylthio-(1H,4H)-1,2,4-triazolin-5-one;

all disclosed in JP 52/125,168.

EXAMPLE A Pre-emergence Test

Solvent: 5 parts by weight of acetone

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent, thestated amount of emulsifier is added and the concentrate is diluted withwater to the desired concentration.

Seeds of the test plants are sown in normal soil and, after 24 hours,watered with the preparation of the active compound. It is expedient tokeep constant the amount of water per unit area. The concentration ofthe active compound in the preparation is of no importance, only theamount of active compound applied per unit area being decisive. Afterthree weeks, the degree of damage to the plants is rated in % damage incomparison to the development of the untreated control. The figuresdenote:

0%=no action (like untreated control)

100%=total destruction.

In this test, for example, the compounds according to the preparationExamples 2, 14, 23, 32, 41, 45, 48 and 57 show a remarkedly betterherbicidal activity against weeds and a remarkedly better selectivity inuseful plants, such as, for example, sugar beets, than the comparisonsubstance (B).

The compounds of Examples 164, 173, 181, 193, 197, 200 and 203 showsimilar good properties.

EXAMPLE B Post-emergence Test

Solvent: 5 parts by weight of acetone

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent, thestated amount of emulsifier is added and the concentrate is diluted withwater to the desired concentration.

Test plants which have a height of 5-15 cm are sprayed with thepreparation of the active compound in such a way as to apply theparticular amounts of active compound desired per unit area. Theconcentration of the spary liquor is so chosen that the particularamounts of active compound desired are applied in 2,000 l of water/ha.After three weeks, the degree of damage to the plants is rated in %damage in comparison to the development of the untreated control. Thefigures denote:

0%=no action (like untreated control)

100%=total destruction

In this test, for example, the compounds according to Examples 1, 2, 3,14, 23, 32, 41, 45, 48, 57 and 78 show a distinctly better herbicidalaction than the comparison substance (A) and (B), respectively incombating mono- and dicotelydon weeds.

The compounds of Examples 175, 181, 182, 193, 197, 199, 200, 201, 202and 203 show similar good properties.

It will be understood that the specification and examples areillustrative but not limitative of the present invention and that otherembodiments within the spirit and scope of the invention will suggestthemselves to those skilled in the art.

We claim:
 1. A substituted triazolinone of the formula ##STR484## inwhich R¹ represents hydrogen, methyl, ethyl, n- or i-propyl, n-, i-, s-or t-butyl, n- or i-pentyl, n- or i-hexyl, cyclopropyl, methoxymethyl,ethoxymethyl or propoxymethyl,R² represents hydrogen, or representsmethyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, allyl, propargyl,straight-chain or branched pentyl, hexyl, heptyl, octyl, butenyl,pentenyl, hexenyl, butynyl, pentynyl or hexynyl each of which isoptionally monosubstituted, disubstituted or trisubstituted by halogen;or additionally represents cyclopropyl, cyclopentyl, cyclohexyl,cyclohexenyl, cyclopropylmethyl, cyclopropylethyl, cyclohexylmethyl,cyclohexylethyl or cycloheptyl which are in each case optionallymonosubstituted, disubstituted or trisubstituted by identical ordifferent substituents from the group consisting of fluorine, chlorine,methyl, ethyl and cyano; or represents benzyl, phenylethyl or phenyl, Xrepresents oxygen or sulphur and Y represent oxygen or sulphur.
 2. Asubstituted triazolinone according to claim 1, in whichR¹ representsn-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl or cyclopropyl,and X and Y represent O.
 3. A substituted triazolinone according toclaim 2, in whichR¹ represents i-propyl, s-butyl or cyclopropyl.
 4. Acompound according to claim 1, wherein such compound is4-amino-1-(N-t-butyl-carbamoyl)-3-methyl-1,2,4-triazolin-5-one of theformula ##STR485##
 5. A compound according to claim 1, wherein suchcompound is4-amino-1-(N-1,2-dimethyl-propyl-carbamoyl)-3-methyl-1,2,4-triazolin-5-oneof the formula ##STR486##
 6. A compound according to claim 1, whereinsuch compound is4-amino-1-(N-monochloro-t-butyl-carbamoyl)-3-methyl-1,2,4-triazolin-5-oneof the formula ##STR487##
 7. A compound according to claim 1, whereinsuch compound is4-amino-1-(N-1,1-dimethyl-propyl-carbamoyl)-3-methyl-1,2,4-triazolin-5-oneof the formula ##STR488##
 8. A compound according to claim 1, whereinsuch compound is4-amino-1-(N-cyclopentyl-carbamoyl)-3-methyl-1,2,4-triazolin-5-one ofthe formula ##STR489##
 9. A compound according to claim 1, wherein suchcompound is4-amino-1-(N-monofluoro-t-butyl-carbamoyl)-3-methyl-1,2,4-triazolin-5-oneof the formula ##STR490##
 10. A compound according to claim 1, whereinsuch compound is4-amino-1-(N-cyclohexyl-carbamoyl)-3-methyl-1,2,4-triazolin-5-one of theformula ##STR491##
 11. A compound according to claim 1, wherein suchcompound is4-amino-1-(N-1,1-dimethyl-propargyl-carbamoyl)-3-methyl-1,2,4-triazolin-5-oneof the formula ##STR492##
 12. A compound according to claim 1, whereinsuch compound is4-amino-1-(N-1,1-dimethyl-pentyl-carbamoyl)-3-methyl-1,2,4-triazolin-5-oneof the formula ##STR493##
 13. A compound according to claim 1, whereinsuch compound is4-amino-1-[N-(chloro-t-butyl)carbamoyl]-3-isopropyl-1,2,4-triazolin-5-oneof the formula ##STR494##
 14. A compound according to claim 1, whereinsuch compound is4-amino-1-(N-t-butylcarbamoyl)-3-isopropyl-1,2,4-triazolin-5-one of theformula ##STR495##
 15. A compound according to claim 1, wherein suchcompound is4-amino-1-(N-isopropylcarbamoyl)-3-isopropyl-1,2,4-triazolin-5-one ofthe formula ##STR496##
 16. A herbicidal composition comprising aherbicidally effective amount of a compound according to claim 1 and aninert diluent.
 17. A method of combating unwanted vegetation whichcomprises applying to such vegetation or to a locus from which it isdesired to exclude such vegetation a herbicidally effective amount of acompound according to claim
 1. 18. The method according to claim 17,wherein such compoundis4-amino-1-(N-t-butyl-carbamoyl)-3-methyl-1,2,4-triazolin-5-one,4-amino-1-(N-1,2-dimethyl-propyl-carbamoyl)-3-methyl-1,2,4-triazolin-5-one,4-amino-1-(N-monochloro-t-butyl-carbamoyl)-3-methyl-1,2,4-triazolin-5-one,4-amino-1-(N-1,1-dimethyl-propyl-carbamoyl)-3-methyl-1,2,4-triazolin-5-one,4-amino-1-(N-cyclopentyl-carbamoyl)-3-methyl-1,2,4-triazolin-5-one,4-amino-1-(N-monofluoro-t-butyl-carbamoyl)-3-methyl-1,2,4-triazolin-5-one,4-amino-1-(N-cyclohexyl-carbamoyl)-3-methyl-1,2,4-triazolin-5-one,4-amino-1-(N-1,1-dimethyl-propargyl-carbamoyl)-3-methyl-1,2,4-triazolin-5-one,4-amino-1-(N-1,1-dimethyl-pentyl-carbamoyl)-3-methyl-1,2,4-triazolin-5-one,4-amino-1-(N-(chloro-t-butyl)carbamoyl)-3-isopropyl-1,2,4-triazolin-5-one,4-amino-1-(N-t-butylcarbamoyl)-3-isopropyl-1,2,4-triazolin-5-one,4-amino-1-(N-(fluoro-t-butyl)carbamoyl)-3-isopropyl-1,2,4-triazolin-5-one,or 4-amino-1-(N-isopropylcarbamoyl)-3-isopropyl-1,2,4-triazolin-5-one.19. A compound according to claim 1, wherein such compound is4-amino-1-[N-(fluoro-t-butyl)carbamoyl]-3-isopropyl-1,2,4-triazolin-5-oneof the formula ##STR497##